Method for producing 4-methyl-1-pentene copolymer compositions, molded articles, mandrels, and rubber hoses.

Abstract

Provided are: a 4-methyl-1-pentene copolymer composition (X) that contains 50-90 parts by mass of a 4-methyl-1-pentene-based polymer (A) in which the melting point measured by DSC falls within a range of 200-250°C, 5-30 parts by mass of a 4-methyl-1-pentene-based polymer (B) in which the melting point measured by DSC is less than 200°C or the melting point is not measured, and 5-30 parts by mass of a thermoplastic elastomer (C) other than (A) and (B) and that satisfies requirements (a) and (b); and a method for manufacturing a molded body and a rubber hose that are formed of the composition (X). Requirement (a): the tanδ peak temperature determined by means of dynamic viscoelasticity measurement at 0-240°C and a frequency of 10 rad / s is 0-60°C. Requirement (b): the tanδ peak value determined by means of dynamic viscoelasticity measurement at 0-100°C and a frequency of 10 rad / s is 0.15-0.8.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a 4-methyl-1-pentene copolymer composition, a molded article, a mandrel, and a rubber hose. [Background technology]

[0002] 4-methyl-1-pentene polymers, whose main constituent monomer is 4-methyl-1-pentene, are widely used in various applications due to their excellent release properties, heat resistance, water resistance, and solvent resistance. For example, 4-methyl-1-pentene polymer films are used as release films for FPCs (Flexible Printed Circuits) and release films for composite material molding, taking advantage of their high melting point and good release properties. Molded articles of 4-methyl-1-pentene polymers are used in laboratory equipment and mandrels, taking advantage of their chemical resistance and water resistance.

[0003] In recent years, with the increasing size and power output of construction machinery, hydraulic hoses have become larger in diameter, and mandrels used in manufacturing have also become larger. This has led to problems with the workability of the mandrels, their pullability during molding, and the fact that the molded bodies made of 4-methyl-1-pentene polymer are rigid when bent during storage in reels, which can cause breakage or chipping. Regarding the pullability of mandrels, techniques for adjusting the surface roughness have been disclosed (see, for example, Patent Document 1).

[0004] On the other hand, 4-methyl-1-pentene polymers are used not only on their own but also in compositions with elastomers. For example, in mandrels, resin compositions containing small amounts of olefin elastomers or liquid olefin oligomers have been disclosed to improve the flexibility of the 4-methyl-1-pentene polymer (see, for example, Patent Documents 2-4). Furthermore, in heat-resistant protectors for automotive cables (see, for example, Patent Document 5) and wire coating materials (see, for example, Patent Document 6), resin compositions containing small amounts of 4-methyl-1-pentene polymers have been disclosed to improve the heat resistance of olefin elastomers. In these applications, the compositions are used near heat-generating elements such as engine compartments and electronic components in automobiles, requiring heat resistance and shape retention. Additionally, in long-term winter use environments, resistance to fracture at low temperatures is necessary.

[0005] Furthermore, compositions of two types of 4-methyl-1-pentene copolymers that meet specific conditions and a thermoplastic resin have also been disclosed, primarily for use in films and hollow molded articles (see, for example, Patent Document 7). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Patent No. 5533519 [Patent Document 2] Japanese Patent Publication No. 2006-274119 [Patent Document 3] Japanese Patent Application Publication No. 11-269330 [Patent Document 4] Japanese Patent Publication No. 2013-249387 [Patent Document 5] Japanese Patent Publication No. 2010-235800 [Patent Document 6] Japanese Patent Publication No. 2002-138173 [Patent Document 7] Patent No. 5769821 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, the resin compositions exemplified in the above-mentioned Patent Documents 1-3 and 7 are either studies using 4-methyl-1-pentene polymers alone, or have a high content of 4-methyl-1-pentene copolymers, resulting in poor fracture resistance at low temperatures due to low-temperature brittleness derived from the 4-methyl-1-pentene polymers. Furthermore, the resin composition disclosed in Patent Document 4 has concerns that the liquid olefin oligomer may bleed out, leading to stickiness and deterioration of mold release properties during repeated use. In addition, the resin compositions disclosed in Patent Documents 5 and 6 have a high content of olefin elastomers, so the addition of a small amount of 4-methyl-1-pentene polymer does not significantly improve heat resistance, resulting in poor high-temperature properties.

[0008] One embodiment of the present invention aims to solve the problem of providing a 4-methyl-1-pentene copolymer composition that can maintain its shape at high temperatures and the resulting molded article exhibits excellent toughness at low temperatures. Another embodiment of the present invention aims to solve the problem of providing a molded article that can maintain its shape at high temperatures and exhibits excellent toughness at low temperatures. [Means for solving the problem]

[0009] One example of a specific measure to solve the above problem is as follows: <1> 50 to 90 parts by mass of a 4-methyl-1-pentene polymer (A) whose melting point is in the range of 200 to 250°C as measured by differential scanning calorimetry (DSC), 5 to 30 parts by mass of a 4-methyl-1-pentene polymer (B) whose melting point is less than 200°C as measured by differential scanning calorimetry (DSC), or in which no melting point is observed, The above-mentioned 4-methyl-1-pentene polymer (A) and thermoplastic elastomer (C) other than the above-mentioned 4-methyl-1-pentene polymer (B) are comprising 5 to 30 parts by mass (the total amount of (A), (B), and (C) being 100 parts by mass), and, A 4-methyl-1-pentene copolymer composition (X) that satisfies the following requirements (a) and (b): Requirement (a): The temperature at which the value of the loss tangent tanδ, determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of 0 to 240°C is maximum is 0°C to 60°C; Requirement (b): The value at which the value of the loss tangent tanδ, determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of 0 to 100°C is maximum is 0.15 to 0.8. <2> The above 4-methyl-1-pentene polymer (A) satisfies the following requirements (c) and (d), and the above 4-methyl-1-pentene polymer (B) satisfies the following requirements (f) and (g), <1> The 4-methyl-1-pentene copolymer composition (X) described above; requirement (c): The constituent units derived from 4-methyl-1-pentene are in the range of 100 to 90 mol%, and the constituent units derived from at least one selected from the group consisting of ethylene and α-olefins having 10 to 20 carbon atoms are in the range of 0 to 10 mol% [provided that the total amount of constituent units derived from 4-methyl-1-pentene and constituent units derived from ethylene and α-olefins having 10 to 20 carbon atoms is 100 mol%]; requirement (d): The density is 820 to 850 kg / m³ 3 It is within the range; requirement (f): It consists of 55 to 97 mol% of constituent unit (i) derived from 4-methyl-1-pentene and 3 to 45 mol% of constituent unit (ii) derived from ethylene and at least one α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (provided that the total of constituent unit (i) and constituent unit (ii) is 100 mol%); requirement (g): The tanδ peak temperature determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150°C is 15°C to 45°C; requirement (h): The density is 830 to 870 kg / m³ 3 It is within the range. <3> The above thermoplastic elastomer (C) is an olefin-based elastomer (C-1) or a styrene-based elastomer (C-2). <1> or <2> The 4-methyl-1-pentene copolymer composition (X) described above. <4> A molded article formed from the 4-methyl-1-pentene copolymer composition (X) according to any one of <1> to <3>. <5> <1> to < 3 > A mandrel formed from the 4-methyl-1-pentene copolymer composition (X) according to any one of <1> to <3>. <6> <1> to < 3 > A step of obtaining a mandrel by extrusion molding the 4-methyl-1-pentene copolymer composition (X) according to any one of <1> to <3>. A step of manufacturing a rubber hose using the mandrel obtained in the above step. A method for manufacturing a rubber hose, including the above steps.

Advantages of the Invention

[0010] According to one embodiment of the present invention, a 4-methyl-1-pentene copolymer composition capable of maintaining its shape at high temperatures and having excellent toughness at low temperatures of the obtained molded article is provided. According to the solution of one embodiment of the present invention, a molded article capable of maintaining its shape at high temperatures and having excellent toughness at low temperatures is provided.

Modes for Carrying Out the Invention

[0011] Hereinafter, the content of the present invention will be described in detail. The description of the content of the constituent elements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, "~" indicating a numerical range is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

[0013] In this specification, the unit described in either one of the front and back of "~" indicating a numerical range means the same unit unless otherwise specified.

[0014] In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0015] In this specification, unless otherwise specified, the term "polymer" includes both homopolymers and copolymers.

[0016] The present invention will be described in detail below. <4-methyl-1-pentene copolymer composition (X)> The 4-methyl-1-pentene copolymer composition (X) according to the present invention comprises 50 to 90 parts by mass of a 4-methyl-1-pentene polymer (A) (hereinafter also simply referred to as "4-methyl-1-pentene polymer (A)") having a melting point (Tm) measured by differential scanning calorimetry (DSC) in the range of 200 to 250°C, 5 to 30 parts by mass of a 4-methyl-1-pentene polymer (B) (hereinafter also simply referred to as "4-methyl-1-pentene polymer (B)") whose melting point is less than 200°C as measured by differential scanning calorimetry (DSC), or whose melting point is not observed, The material comprises 5 to 30 parts by mass of the above-mentioned 4-methyl-1-pentene polymer (A) and a thermoplastic elastomer (C) other than the above-mentioned 4-methyl-1-pentene polymer (B) (the total amount of (A), (B), and (C) being 100 parts by mass), and satisfies the following requirements (a) and (b).

[0017] The 4-methyl-1-pentene copolymer composition (X) according to the present invention, having the above configuration, results in a molded article that maintains heat resistance while exhibiting excellent flexibility at room temperature and toughness at low temperatures. The reason for this is not clear, but it is presumed to be as follows.

[0018] The 4-methyl-1-pentene copolymer composition (X) contains 4-methyl-1-pentene polymers (A) and 4-methyl-1-pentene polymer (B), which have different melting points. Therefore, it is possible to soften it more effectively than other thermoplastic elastomers while maintaining the heat resistance that is a characteristic of 4-methyl-1-pentene polymers. This allows for shape retention at high temperatures, and it is also expected to have excellent toughness at low temperatures due to its good dispersibility with thermoplastic elastomers.

[0019] Furthermore, since the molded article made of the 4-methyl-1-pentene copolymer composition (X) of the present invention has the above-mentioned structure, it has appropriate elongation and hardness, and when the molded article is a mandrel, it can exhibit release properties without the mandrel deforming when it is pulled out after rubber hose manufacturing.

[0020] The 4-methyl-1-pentene copolymer composition (X) according to the present invention satisfies both of the following requirements (a) and (b). <<Requirement(a)>> The 4-methyl-1-pentene copolymer composition (X) has a temperature range of 0 to 240°C at which the value of the loss tangent tanδ, determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz), is maximum (hereinafter also referred to as the "tanδ peak temperature") is between 0°C and 60°C.

[0021] Here, the lower limit of the tanδ peak temperature in the temperature range of 0 to 240°C is preferably 5°C or higher, and more preferably 10°C or higher. The upper limit of the tanδ peak temperature is preferably 55°C or lower, more preferably 50°C or lower, and particularly preferably 45°C or lower. When the tanδ peak temperature in the temperature range of 0 to 240°C is within the above temperature range, the molded articles and mandrels obtained from the 4-methyl-1-pentene copolymer composition (X) can achieve both extensibility and flexibility.

[0022] Further details regarding the dynamic viscoelasticity measurement method are as described in the examples below. <<Requirement (b)>> The 4-methyl-1-pentene copolymer composition (X) exhibits a maximum loss tangent tanδ value (hereinafter also referred to as the "tanδ peak value") of 0.15 to 0.8, obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of 0 to 100°C.

[0023] If the tanδ peak value in the temperature range of 0 to 100°C falls within the above temperature range, the rubber hose will change flexibly to slow deformations such as bending, and will become harder to withstand the rapid deformation of the mandrel that occurs when the manufactured rubber hose is pulled out of the mandrel by hand or compressed air, making it easier to pull out.

[0024] From the above viewpoint, the lower limit of the tanδ peak value in the temperature range of 0 to 100°C is preferably 0.16 or higher, and more preferably 0.20 or higher. From a similar viewpoint, the upper limit of the tanδ peak value in the temperature range of 0 to 100°C is preferably 0.8 or lower, more preferably 0.5 or lower, and even more preferably 0.4 or lower.

[0025] Furthermore, the tanδ peak temperature and tanδ peak value can be adjusted by the composition and content of the 4-methyl-1-pentene polymer (A) and 4-methyl-1-pentene polymer (B), as described later.

[0026] The following describes each of the constituent elements of the 4-methyl-1-pentene copolymer composition (X) according to the present invention: the 4-methyl-1-pentene polymer (A), the 4-methyl-1-pentene polymer (B), and the thermoplastic elastomer (C) other than the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene polymer (B) (hereinafter also simply referred to as "thermoplastic elastomer (C)"). <4-methyl-1-pentene polymer (A)> A 4-methyl-1-pentene polymer (A) having a melting point (Tm) measured by differential scanning calorimetry (DSC) in the range of 200 to 250°C is not particularly limited as long as its melting point measured by differential scanning calorimetry (DSC) is in the range of 200 to 250°C. It may be a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and an α-olefin other than 4-methyl-1-pentene.

[0027] If the melting point of the 4-methyl-1-pentene polymer (A), as measured by differential scanning calorimetry (DSC), is 200°C or higher, the strength of molded articles obtained using a resin composition containing the 4-methyl-1-pentene polymer (A) can be improved. Furthermore, if the melting point is 250°C or lower, the impact strength and toughness of molded articles obtained using a resin composition containing the 4-methyl-1-pentene polymer (A) can be improved.

[0028] From the above viewpoint, the 4-methyl-1-pentene polymer (A) preferably has a melting point (Tm) measured by differential scanning calorimetry (DSC) in the range of 210 to 245°C, more preferably 220 to 240°C.

[0029] The melting point is measured using a differential scanning calorimeter, for example, as follows: 3-7 mg of the sample is sealed in an aluminum pan and heated from room temperature to 280°C at a rate of 10°C / min. The sample is then held at 300°C for 5 minutes to completely melt it. Next, it is cooled to -50°C at a rate of 10°C / min, left at -50°C for 5 minutes, and then heated again to 300°C at a rate of 10°C / min. The peak temperature obtained during this second heating test is taken as the melting point (Tm).

[0030] The melting points of the 4-methyl-1-pentene polymer (B) and the olefin polymer (C), described later, can also be measured using the same method.

[0031] From the viewpoint of maintaining shape at high temperatures and having excellent toughness at low temperatures in the resulting molded article, it is preferable that the 4-methyl-1-pentene polymer (A) satisfies the following requirements (c) and (d). <<Requirement(c)>> Preferably, the constituent units derived from 4-methyl-1-pentene (hereinafter sometimes referred to as "constituent unit (i)") are in the range of 100 to 90 mol% (preferably 99.9 to 92 mol%, more preferably 99 to 95 mol%), and the constituent units derived from ethylene and at least one selected from α-olefins having 10 to 20 carbon atoms (hereinafter sometimes referred to as "constituent unit (iii)") are in the range of 0 to 10 mol% (preferably 0.1 to 8 mol%, more preferably 1 to 5 mol%) [however, the total amount of constituent units derived from 4-methyl-1-pentene and constituent units derived from ethylene and α-olefins having 10 to 20 carbon atoms shall be 100 mol%].

[0032] In this specification, the structural unit derived from α-olefin refers to the structural unit corresponding to α-olefin, i.e., the structural unit represented by -CH2-CHR- (where R is a hydrogen atom or an alkyl group). The structural unit derived from 4-methyl-1-pentene can be similarly interpreted and refers to the structural unit corresponding to 4-methyl-1-pentene (i.e., the structural unit represented by -CH2-CH(-CH2CH(CH3)2)-).

[0033] Examples of α-olefins having 10 to 20 carbon atoms that can copolymerize with 4-methyl-1-pentene include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. These α-olefins having 10 to 20 carbon atoms may be used individually or in combination of two or more. <<Requirement(d)>> The density of the 4-methyl-1-pentene polymer (A) is preferably 820-850 kg / m³. 3 , more preferably 825-845 kg / m 3 More preferably 830-840 kg / m 3 It is within the range.

[0034] When the 4-methyl-1-pentene polymer (A) satisfies the above requirements (c) and (d), it exhibits excellent heat resistance, and the molded article obtained from such polymer (A) has an excellent balance with mold release properties.

[0035] The 4-methyl-1-pentene polymer (A) preferably satisfies the following requirement (e) in addition to the above requirements (c) and (d). <<Requirement(e)>> The 4-methyl-1-pentene polymer (A) has a melt flow rate (MFR) measured at a temperature of 260°C and a load of 5.0 kgf (49.03 N) in accordance with ASTM D1238, preferably 1 to 200 g / 10 min, more preferably 5 to 100 g / 10 min, and even more preferably 10 to 60 g / 10 min.

[0036] From the viewpoint of maintaining shape at high temperatures and providing the resulting molded article with excellent toughness at low temperatures, the 4-methyl-1-pentene polymer (A) preferably has a temperature (tanδ peak temperature) at which the value of the loss tangent tanδ, determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz), is maximized in the temperature range of 0 to 240°C, preferably 0 to 60°C, more preferably 5 to 55°C, and even more preferably 10 to 50°C.

[0037] Furthermore, from the viewpoint of maintaining shape at high temperatures and having excellent toughness at low temperatures in the resulting molded article, the 4-methyl-1-pentene polymer (A) preferably has a maximum loss tangent tanδ value (tanδ peak value) obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of 0 to 100°C, which is 0.05 to 0.8, more preferably 0.05 to 0.5, and even more preferably 0.07 to 0.4.

[0038] Further details regarding the dynamic viscoelasticity measurement method are as described in the examples below.

[0039] The content of 4-methyl-1-pentene polymer (A) is 50 to 90 parts by mass per 100 parts by mass of the total of (A), (B), and (C).

[0040] When the content of 4-methyl-1-pentene polymer (A) is 50 parts by mass or more, the molded article obtained from the 4-methyl-1-pentene copolymer composition (X) can exhibit the heat resistance inherent to the 4-methyl-1-pentene polymer. Furthermore, when the content of 4-methyl-1-pentene polymer (A) is 90 parts by mass or less, the composition can contain a large amount of the 4-methyl-1-pentene polymer (B) and thermoplastic elastomer (C) described later. Molded articles obtained from such resin compositions exhibit excellent toughness at low temperatures, become flexible, suppress cracking at room temperature, and have excellent tensile properties.

[0041] From the above viewpoint, the upper limit of the content of 4-methyl-1-pentene polymer (A) is preferably 80 parts by mass per 100 parts by mass of the total of (A), (B), and (C). The lower limit of the content of 4-methyl-1-pentene polymer (A) is preferably 55 parts by mass, and more preferably 60 parts by mass, per 100 parts by mass of the total of (A), (B), and (C).

[0042] The 4-methyl-1-pentene polymer (A) can be produced by known methods, for example, the method for producing the 4-methyl-1-pentene polymer (B) described later. <4-methyl-1-pentene polymer (B)> A 4-methyl-1-pentene polymer (B) whose melting point measured by differential scanning calorimetry (DSC) is less than 200°C or whose melting point is not observed is not particularly limited, and may be a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and an α-olefin other than 4-methyl-1-pentene.

[0043] The 4-methyl-1-pentene polymer (B) has a melting point of less than 200°C or no melting point is observed by differential scanning calorimetry (DSC), which allows for high flexibility to be imparted to molded articles obtained from the 4-methyl-1-pentene copolymer composition (X).

[0044] From the above viewpoint, it is preferable that the 4-methyl-1-pentene polymer (B) has a melting point of 160°C or less or no melting point is observed by differential scanning calorimetry (DSC), more preferably a melting point of 150°C or less or no melting point is observed, and even more preferably a melting point of 150°C or less.

[0045] From the above viewpoint, it is preferable that the 4-methyl-1-pentene polymer (B) has a lower limit of melting point of 110°C or higher as measured by differential scanning calorimetry (DSC), or that no melting point is observed, more preferably that the melting point is 110°C or higher, and even more preferably that the melting point is 130°C or higher.

[0046] From the viewpoint of maintaining shape at high temperatures and having excellent toughness at low temperatures in the resulting molded article, the 4-methyl-1-pentene polymer (B) preferably satisfies one or more of the following requirements (f) to (j), more preferably two or more, even more preferably three or more, and particularly preferably all of them. <<Requirement(f)>> It consists of 55-97 mol% of a constituent unit derived from 4-methyl-1-pentene (hereinafter sometimes referred to as "constituent unit (i)") and 3-45 mol% of a constituent unit derived from ethylene and at least one α-olefin having 3-20 carbon atoms (excluding 4-methyl-1-pentene) (hereinafter sometimes referred to as "constituent unit (ii)") (the sum of constituent unit (i) and constituent unit (ii) is 100 mol%).

[0047] The above requirement (f) specifies that the 4-methyl-1-pentene polymer (B) has in a specific proportion a constituent unit (i) derived from 4-methyl-1-pentene and a constituent unit (ii) derived from ethylene and at least one α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).

[0048] Specific examples of the above-mentioned α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-octadecene, and 1-hexadecene. Among these, the constituent unit (ii) is preferably at least one selected from ethylene, propylene, and 1-butene.

[0049] The constituent unit (ii) may be a single unit or two or more units may be used in combination.

[0050] Regarding the above 4-methyl-1-pentene polymer (B), the lower limit of the content of constituent units derived from 4-methyl-1-pentene is preferably 55 mol% or more, more preferably 65 mol% or more, and even more preferably 68 mol% or more. On the other hand, the upper limit of the content of constituent units derived from 4-methyl-1-pentene is preferably 97 mol% or less, more preferably 93 mol% or less, and even more preferably 87 mol% or less.

[0051] In the above 4-methyl-1-pentene polymer (B), if the content of the constituent unit (i) derived from 4-methyl-1-pentene is above the lower limit, the tanδ peak temperature determined by dynamic viscoelasticity measurement will be near room temperature, making it easy to adjust the tanδ peak temperature of the 4-methyl-1-pentene copolymer composition (X) to within the aforementioned range. On the other hand, if the content of the constituent unit (i) derived from 4-methyl-1-pentene is below the upper limit, it exhibits relaxation at room temperature.

[0052] From the above viewpoint, in the 4-methyl-1-pentene polymer (B), the upper limit of the content of constituent unit (ii) derived from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is preferably 45 mol% or less, more preferably 35 mol% or less, and even more preferably 32 mol% or less.

[0053] Furthermore, the lower limit of the content of constituent unit (ii) derived from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is preferably 3 mol% or more, more preferably 7 mol% or more, and even more preferably 13 mol% or more.

[0054] The content (mol%) values ​​of each constituent unit of the above 4-methyl-1-pentene polymer (A) and 4-methyl-1-pentene polymer (B) are: 13 The measurement is performed by 13C-NMR. Details of the measurement method are described in the examples below.

[0055] When the above-mentioned structural unit (ii) is a structural unit derived from propylene, the tanδ peak temperature can be set within the above range, and the 4-methyl-1-pentene copolymer composition (X) is likely to yield a molded article that is given flexibility and extensibility when used as a mandrel.

[0056] From the above viewpoint, it is preferable that the 4-methyl-1-pentene polymer (B) consists only of the above-mentioned structural unit (i) and the above-mentioned structural unit (ii). <<Requirements (g)>> The 4-methyl-1-pentene polymer (B) preferably has a tanδ peak temperature of 15°C to 45°C, more preferably 20°C to 45°C, and even more preferably 25°C to 45°C, as determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150°C.

[0057] When the tanδ peak temperature is within the above range in the temperature range of -40 to 150°C, the molded body obtained from the 4-methyl-1-pentene copolymer composition (X) has a hardness change near room temperature and becomes easily softened. At the same time, when the mandrel is pulled out from the manufactured rubber hose, the storage modulus increases and becomes hard due to the rapid deformation of the mandrel, so that the drawability can be improved.

[0058] Details of the dynamic viscoelasticity measurement method are as described in the examples described later. <<Requirement (h)>> The density of the 4-methyl-1-pentene polymer (B) is preferably 830 to 870 kg / m 3 More preferably 830 to 860 kg / m 3 Even more preferably 830 to 850 kg / m 3 is. Details of the measurement method are as described in the examples described later.

[0059] The density of the 4-methyl-1-pentene polymer (B) can be appropriately changed depending on the comonomer composition ratio of the 4-methyl-1-pentene·α-olefin copolymer. When the density of the 4-methyl-1-pentene polymer (B) is within the above range, the transparency and mold release property are good.

[0060] From the viewpoint of being able to maintain the shape at high temperature and excellent toughness of the obtained molded body at low temperature, the 4-methyl-1-pentene polymer (B) preferably satisfies one or more of requirements (i) to (k), more preferably satisfies two or more of requirements (i) to (k), and even more preferably satisfies all of requirements (i) to (k). <<Requirement (i)>> The 4-methyl-1-pentene polymer (B) preferably has an intrinsic viscosity [η] in decalin at 135°C in a decalin in the range of 0.1 to 5.0 dl / g, more preferably 0.5 to 4.0 dl / g, and even more preferably 1.0 to 3.5 dl / g. As described later, the molecular weight can be controlled by using hydrogen during polymerization, allowing for the free acquisition of low-molecular-weight to high-molecular-weight polymers and adjustment to the above-mentioned range of intrinsic viscosity [η]. Details of the measurement method are as described in the examples below. <<Requirements(j)>> The 4-methyl-1-pentene polymer (B) preferably has a weight-average molecular weight (Mw) of 1,000 to 1,000,000, more preferably 5,000 to 800,000, and even more preferably 10,000 to 500,000, measured by gel permeation chromatography (GPC), in terms of polystyrene. Details of the measurement method are as described in the examples below.

[0061] The 4-methyl-1-pentene polymer (B) preferably has a molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), measured by gel permeation chromatography (GPC), in the range of 1.0 to 3.5, more preferably 1.2 to 3.0, and even more preferably 1.5 to 2.8 or less. A molecular weight distribution (Mw / Mn) of 3.5 or less is preferable because it reduces the influence of low molecular weight polymers and low stereoregularity polymers derived from the composition distribution, and the resulting molded article is less likely to suffer a decrease in mechanical strength. <<Requirements(k)>> The melt flow rate (MFR; compliant with ASTM D1238, at a temperature of 230°C and a load of 2.16 kgf (21.18 N)) of the 4-methyl-1-pentene polymer (B) is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and even more preferably within the range of 1.0 to 30 g / 10 min.

[0062] When the melt flow rate (MFR) of the 4-methyl-1-pentene polymer (B) is above the lower limit within the above range, good fluidity is obtained, and good dispersibility with the 4-methyl-1-pentene polymer (A) is achieved.

[0063] If the value is below the upper limit of the aforementioned range, it is preferable because the molecular weight of the 4-methyl-1-pentene polymer (B) is not too small, and sufficient mechanical strength can be obtained in the resulting molded article.

[0064] The content of 4-methyl-1-pentene polymer (B) is 5 to 30 parts by mass per 100 parts by mass of the total of (A), (B), and (C) above. When the content of polymer (B) is within the above range, the compatibility with 4-methyl-1-pentene polymer (A) is improved, and 4-methyl-1-pentene polymer (A) can be efficiently softened with a small amount of addition. Furthermore, the extractability of the resulting molded article tends to improve due to the effect of 4-methyl-1-pentene polymer (B).

[0065] From the above viewpoint, the lower limit of the content of 4-methyl-1-pentene polymer (B) is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more, based on 100 parts by mass of the total of (A), (B), and (C). The upper limit of the content of 4-methyl-1-pentene polymer (B) is preferably 25 parts by mass or less, based on 100 parts by mass of the total of (A), (B), and (C). <Method for producing 4-methyl-1-pentene polymer (B)> The method for producing the 4-methyl-1-pentene polymer (B) is not particularly limited, but for example, if 4-methyl-1-pentene satisfies the above requirement (f), it can be produced by polymerizing the above ethylene and an α-olefin having 3 to 20 carbon atoms (except 4-methyl-1-pentene) in the presence of a suitable polymerization catalyst such as a magnesium-supported titanium catalyst or a metallocene catalyst.

[0066] Suitable polymerization catalysts that can be used here include conventionally known catalysts, such as magnesium-supported titanium catalysts, metallocene catalysts described in International Publication No. 01 / 53369, International Publication No. 01 / 27124, Japanese Patent Publication No. 3-193796, or Japanese Patent Publication No. 2-41303, International Publication No. 2011 / 055803, International Publication No. 2014 / 050817, etc. Polymerization can be carried out by appropriately selecting from liquid-phase polymerization methods, including dissolution polymerization and suspension polymerization, as well as gas-phase polymerization methods.

[0067] In liquid-phase polymerization, an inert hydrocarbon solvent can be used as the solvent constituting the liquid phase. Examples of the above inert hydrocarbons include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane; and mixtures thereof.

[0068] Furthermore, in liquid-phase polymerization, bulk polymerization can also be carried out using the monomer corresponding to the constituent unit (i) derived from 4-methyl-1-pentene (i.e., 4-methyl-1-pentene) as the solvent, or the monomer corresponding to the constituent unit (ii) derived from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) as the solvent.

[0069] Furthermore, by performing stepwise copolymerization of the above-mentioned 4-methyl-1-pentene with the above-mentioned ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), the compositional distribution of constituent units (i) and (ii) can be appropriately controlled.

[0070] The polymerization temperature is preferably -50 to 200°C, more preferably 0 to 100°C, and even more preferably 20 to 100°C. The polymerization pressure is preferably atmospheric pressure to 10 MPa gauge pressure, and more preferably atmospheric pressure to 5 MPa gauge pressure.

[0071] During polymerization, hydrogen may be added to control the molecular weight and polymerization activity of the resulting polymer. The appropriate amount of hydrogen to add is approximately 0.001 to 100 NL per 1 kg of the total amount of 4-methyl-1-pentene and ethylene and α-olefins with 3 to 20 carbon atoms (excluding 4-methyl-1-pentene). <Thermoplastic elastomer (C)> The 4-methyl-1-pentene copolymer composition (X) includes the above 4-methyl-1-pentene polymer (A) and a thermoplastic elastomer (C) other than the above 4-methyl-1-pentene polymer (B).

[0072] Thermoplastic elastomers (C) refer to polymers that exhibit thermoplastic properties when heated above their melting point, while showing rubber elasticity at room temperature.

[0073] The thermoplastic elastomer (C) is not particularly limited as long as it is a polymer other than the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene polymer (B) described above, but specifically, olefin-based elastomers (C-1) and styrene-based elastomers (C-2) are preferred. <<Olefin-based elastomer (C-1)>> A first embodiment of the olefin-based elastomer (C-1) is a copolymer of one selected from the group consisting of ethylene and propylene and at least one selected from the group consisting of butadiene, hydrogenated butadiene, isoprene, hydrogenated isopreneisobutylene, and α-olefin.

[0074] The copolymerization can be either block copolymerization or graft copolymerization, but in the case of a copolymer consisting of one selected from the group consisting of ethylene and propylene and an α-olefin, the copolymerization may be random copolymerization.

[0075] The above-mentioned α-olefin refers to an olefin having a double bond at one end of its molecular chain, and 1-butene and 1-octene are preferably used.

[0076] Examples of olefin-based elastomers (C-1) include block copolymers of a polyolefin block forming a highly crystalline polymer such as polypropylene for the rigid part and an amorphous monomer copolymer for the soft part. Specifically, examples include olefin (crystalline)-ethylene-butylene-olefin block copolymer and propylene-olefin (amorphous)-propylene block copolymer.

[0077] Specific examples include products marketed under the names DYNARON (registered trademark) by ENEOS Material Corporation, Toughmer (registered trademark) and Toughmer PN (registered trademark) by Mitsui Chemicals, Inc., ENGAGE (registered trademark) and VERSIFY (registered trademark) by Dow Chemical Ltd., and Vistamaxx (registered trademark) by ExxonMobil Chemicals Ltd.

[0078] A second embodiment of the olefin-based elastomer is a blend of one selected from the group consisting of ethylene and propylene, and one selected from the group consisting of ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-butene copolymer, and hydrogenated styrene-butadiene. In such a blend, the ethylene-propylene copolymer, ethylene-propylene-diene copolymer, and ethylene-butene copolymer may be partially or completely crosslinked.

[0079] Specific examples of olefin-based elastomers include those marketed under the trade names: Milastomer (registered trademark) by Mitsui Chemicals, Inc., Esporex (registered trademark) by Sumitomo Chemical Co., Ltd., Thermolan (registered trademark) and Zelas (registered trademark) by Mitsubishi Chemical Corporation, and Santoprene (registered trademark) by Celanese.

[0080] Furthermore, the olefin-based elastomer according to the present invention may be modified with at least one functional group selected from the group consisting of acid anhydride groups, carboxyl groups, amino groups, imino groups, alkoxysilyl groups, silanol groups, silyl ether groups, hydroxyl groups, and epoxy groups. <<Styrene-based elastomer (C-2)>> Examples of styrene-based elastomers (C-2) include block copolymers (SBS) of a polystyrene block forming the hard part (crystalline part) and a diene monomer block forming the soft part, hydrogenated styrene-butadiene-styrene block copolymer (HSBR), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene-styrene copolymer (SIBS), and styrene-isobutylene copolymer (SIB).

[0081] The styrene-based elastomer may be used alone or in combination of two or more types.

[0082] Specific examples of hydrogenated styrene-butadiene-styrene block copolymers include those commercially available from ENEOS Material Corporation under the trade name Dynalon (registered trademark).

[0083] Styrene-ethylene-propylene-styrene block copolymers are produced by hydrogenating styrene-isoprene-styrene block copolymers (SIS). Specific examples of SIS include those sold by ENEOS Material Corporation under the trade name SIS (registered trademark), by Kuraray Co., Ltd. under the trade name Hybler (registered trademark), and by Kraton Polymer Japan Co., Ltd. under the trade name Kraton D (registered trademark).

[0084] Furthermore, specific examples of styrene-ethylene-propylene-styrene block copolymer (SEPS) include those sold by Kuraray Co., Ltd. under the trade name Septon (registered trademark), and by Kraton Polymer Japan Co., Ltd. under the trade name Kraton (registered trademark).

[0085] Furthermore, specific examples of SEBS include those sold by Asahi Kasei Corporation under the product name ToughTec (registered trademark), and those sold by Kraton Polymer Japan Co., Ltd. under the product name Kraton (registered trademark).

[0086] Furthermore, specific examples of styrene-isobutylene copolymers (SIB) and styrene-isobutylene-styrene copolymers (SIBS) include those commercially available from Kaneka Corporation under the trade name: Sibstar (registered trademark).

[0087] From the viewpoint of enabling shape retention at high temperatures and providing excellent toughness of the resulting molded article at low temperatures, the melt flow rate (MFR; compliant with ASTM D1238, at a temperature of 230°C and a load of 2.16 kgf (21.18 N)) of the thermoplastic elastomer (C) is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and even more preferably within the range of 1.0 to 30 g / 10 min.

[0088] From the viewpoint of maintaining shape at high temperatures and having excellent toughness at low temperatures in the resulting molded article, it is preferable that the thermoplastic elastomer (C) has a melting point of less than 200°C or no melting point is observed as measured by differential scanning calorimetry (DSC), and more preferably that it has a melting point of 160°C or less or no melting point is observed.

[0089] Further details regarding differential scanning calorimetry are as described in the examples below.

[0090] The content of thermoplastic elastomer (C) is 5 to 30 parts by mass per 100 parts by mass of the total of (A), (B), and (C) above.

[0091] When the content of thermoplastic elastomer (C) is within the above range, flexibility at room temperature and toughness at low temperatures will be improved.

[0092] From the above viewpoint, the lower limit of the content of thermoplastic elastomer (C) is preferably 10 parts by mass or more per 100 parts by mass of the total amount of (A), (B), and (C). The upper limit of the content of thermoplastic elastomer (C) is preferably 25 parts by mass or less per 100 parts by mass of the total amount of (A), (B), and (C). <<Other ingredients>> The 4-methyl-1-pentene copolymer composition (X) may, in addition to the above-mentioned 4-methyl-1-pentene polymer (A), 4-methyl-1-pentene polymer (B), and thermoplastic elastomer (C), contain other resins or polymers and / or resin additives (hereinafter also referred to as "other components") other than the above-mentioned 4-methyl-1-pentene polymer (A), 4-methyl-1-pentene polymer (B), and thermoplastic elastomer (C), depending on its application, to the extent that they do not impair the effects of the present invention.

[0093] Examples of such resin additives include pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, UV absorbers, antibacterial agents, surfactants, antistatic agents, weather stabilizers, heat stabilizers, anti-slip agents, anti-blocking agents, foaming agents, crystallization aids, anti-fogging agents, (transparent) nucleating agents, anti-aging agents, hydrochloric acid absorbers, impact modifiers, crosslinking agents, co-crosslinking agents, crosslinking aids, adhesives, softeners, and processing aids. These additives can be used individually or in combination of two or more as appropriate.

[0094] Other resins or polymers that can be added include polystyrene, acrylic resin, polyphenylene sulfide resin, polyether ether ketone resin, polyester resin, polysulfone, polyphenylene oxide, polyimide, polyetherimide, acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-α-olefin copolymer rubber, conjugated diene rubber, phenolic resin, melamine resin, polyester resin, silicone resin, and epoxy resin. The content of these resins or polymers is preferably 0.1 to 30% by mass relative to the total mass of the olefin polymer composition (M).

[0095] Examples of pigments include inorganic pigments (titanium dioxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of dyes include azo type, anthraquinone type, triphenylmethane type, etc. The content of these pigments and dyes is not particularly limited, but is preferably 5% by mass or less, and more preferably 0.1 to 3% by weight, relative to the total mass of the olefin polymer composition (M).

[0096] Examples of fillers include glass fibers, carbon fibers, silica fibers, metal (stainless steel, aluminum, titanium, copper, etc.) fibers, carbon black, silica, glass beads, silicates (calcium silicate, talc, clay, etc.), metal oxides (iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate), and various metal (magnesium, silicon, aluminum, titanium, copper, etc.) powders, mica, glass flakes, etc. These fillers may be used individually or in combination of two or more types.

[0097] Examples of lubricants include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide).

[0098] Examples of plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetyl ricinolate), aliphatic dialbonate esters (such as adipic acid-propylene glycol polyesters), aliphatic tricarboxylic acid esters (such as triethyl citrate), phosphate triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

[0099] Examples of mold release agents include lower (C1-C4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (C4-C30) (such as hydrogenated castor oil), glycol esters of fatty acids, and liquid paraffin.

[0100] Examples of antioxidants include phenolic antioxidants (such as 2,6-di-t-butyl-4-methylphenol), polycyclic phenolic antioxidants (such as 2,2'-methylenebis(4-methyl-6-t-butylphenol)), phosphorus-based antioxidants (such as tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate), and amine-based antioxidants (such as N,N-diisopropyl-p-phenylenediamine).

[0101] Examples of flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.).

[0102] Examples of UV absorbers include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based types.

[0103] Examples of antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodines.

[0104] Examples of surfactants include nonionic, anionic, cationic, or amphoteric surfactants.

[0105] Examples of nonionic surfactants include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyhydric alcohol-type nonionic surfactants such as fatty acid esters of polyethylene oxide and glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and aliphatic amides of alkanolamines. Examples of anionic surfactants include sulfate ester salts of alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates, and phosphate ester salts such as higher alcohol phosphate ester salts. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethyl betaine and higher alkyldihydroxyethyl betaine.

[0106] Examples of antistatic agents include the surfactants mentioned above, fatty acid esters, and polymeric antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymeric antistatic agents include polyether ester amides.

[0107] The content of the various additives mentioned above, such as fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, and antistatic agents, is not particularly limited as long as it does not impair the purpose of the present invention, but is preferably 0.1 to 30% by mass of each additive based on the total mass of the 4-methyl-1-pentene copolymer composition (X). [Method for producing 4-methyl-1-pentene copolymer composition (X)] The method for producing the 4-methyl-1-pentene copolymer composition (X) is not particularly limited, but for example, it may be obtained by mixing a 4-methyl-1-pentene polymer (A), a 4-methyl-1-pentene polymer (B), a thermoplastic elastomer (C), and other optional components in the above-mentioned addition ratios, and then melt-kneading them.

[0108] The method of melt kneading is not particularly limited and can be carried out using commercially available melt kneading equipment such as extruders. For example, the cylinder temperature of the part of the kneading machine is usually preferably 220 to 300°C, more preferably 250 to 290°C. If the temperature is 220°C or higher, melt kneading can be carried out sufficiently and the physical properties of the 4-methyl-1-pentene copolymer composition (X) can be improved. On the other hand, if the cylinder temperature is higher than 300°C or lower, the thermal decomposition of the 4-methyl-1-pentene polymer (A), the 4-methyl-1-pentene polymer (B), and the thermoplastic elastomer (C) can be suppressed. The kneading time is usually preferably 0.1 to 30 minutes, particularly preferably 0.5 to 5 minutes. If the mixing time is 0.1 minutes or longer, sufficient melt mixing can be performed, and if the mixing time is 30 minutes or less, the thermal decomposition of the 4-methyl-1-pentene polymer (A), the 4-methyl-1-pentene polymer (B), and the thermoplastic elastomer (C) can be suppressed. <Molded body> The molded article according to the present invention is preferably made of the above-mentioned 4-methyl-1-pentene copolymer composition (X). There are no particular restrictions on the above-mentioned molded article, and examples include extruded articles and injection-molded articles.

[0109] The method for manufacturing the molded article is not particularly limited; for example, conventionally known manufacturing methods can be used, such as extrusion molding, compression molding, injection molding, 3D printing, and microwave heat molding. Among these molding methods, extrusion molding or injection molding is preferred.

[0110] Applications of molded products include, for example, mandrels and sheaths, as well as automotive parts (front end, fan shroud, cooling fan, engine under cover, engine cover, radiator box, side door, back door inner, back door outer, exterior panel, roof rail, door handle, luggage box, wheel cover, handle, cooling module, air cleaner, spoiler, fuel tank, platform and side member, motor connector housing, bumper, instrument panel surface material, control cable sheathing, wire sheathing), home appliance materials and parts, electrical and electronic components, building materials, civil engineering components, agricultural materials, and daily necessities.

[0111] Among these, the molded product is preferably a mandrel, and more preferably a mandrel for rubber hose manufacturing. The mandrel is preferably formed from the 4-methyl-1-pentene copolymer composition (X).

[0112] The molded article made of the 4-methyl-1-pentene copolymer composition (X) according to the present invention is preferably a mandrel, and more preferably a mandrel for manufacturing rubber hoses. The mandrel according to the present invention satisfies specific requirements (a) and (b), and in particular, even when a large-diameter mandrel is wound onto a reel at room temperature, it has good processability without becoming flexible, cracking or chipping, and sufficient toughness even at low temperatures. Furthermore, when the manufactured rubber hose is pulled out by hand or compressed air, the tanδ peak temperature and peak value are within an appropriate range, so that the mandrel hardens due to rapid deformation when pulled out of the manufactured rubber hose, making it less likely for dimensional changes to occur during pulling out and allowing it to be easily pulled out.

[0113] The mandrel according to the present invention is formed in a continuous cylindrical shape. From the viewpoint of efficiently manufacturing rubber hoses, the length of the mandrel is generally 100m or more, preferably 200m or more. Since the rubber hose is cut to the desired length after the mandrel is pulled out of the resulting rubber hose, it is preferable that the mandrel is formed to be as long as possible, as this allows each process, such as vulcanization, to be carried out continuously, thereby improving productivity.

[0114] Furthermore, the inner diameter of the rubber hose is designed to match the diameter of the mandrel. Generally, the diameter of the mandrel is 2 to 30 mm, preferably 3 to 28 mm.

[0115] Furthermore, the dimensional accuracy of the mandrel requires, for example, a tolerance (i.e., the difference between the maximum and minimum allowable dimensional error) of less than ±0.18 mm relative to the diameter of the mandrel, and preferably less than ±0.15 mm. <Manufacturing method for rubber hoses> These molded articles can be manufactured, for example, by the method shown below.

[0116] The method for manufacturing a rubber hose according to the present invention preferably includes the steps of: obtaining a mandrel by extruding the 4-methyl-1-pentene copolymer composition (X); and manufacturing a rubber hose using the mandrel obtained in the above step. It is even more preferable to include the steps of: obtaining a mandrel by injection molding the 4-methyl-1-pentene copolymer composition (X); inserting an unvulcanized rubber hose into the mandrel obtained in the above step and performing a vulcanization treatment to obtain a vulcanized rubber hose; and withdrawing the vulcanized rubber hose from the mandrel.

[0117] More specifically, the method for manufacturing a rubber hose involves, for example, supplying an unvulcanized rubber composition to form the inner rubber layer to an extrusion molding machine equipped with a crosshead, and obtaining a mandrel with the crosshead perpendicular to the extrusion direction. While extruding and moving the obtained mandrel, the unvulcanized rubber composition may be uniformly covered with the outer circumference of the mandrel to the desired thickness to form an unvulcanized rubber composition layer. Then, if necessary, two layers of reinforcing material are wrapped around the outside of these unvulcanized rubber composition layers or intersecting each other. Furthermore, the outer layer of the unvulcanized rubber composition layer may be covered with rubber material using another extrusion molding machine. Subsequently, a vulcanization reaction is carried out using appropriate equipment such as a high-temperature steam furnace or a continuous oven. In the case of rubber crosslinking (vulcanization) using sulfur, the temperature of the vulcanization reaction is typically 160°C. Finally, the rubber hose is obtained by applying water pressure to the mandrel and pulling it out. [Examples]

[0118] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0119] The methods for measuring the physical properties of the compositions, the polymers used, the methods for preparing test specimens, and the evaluation methods in the following examples and comparative examples are as follows. [Method for measuring the physical properties of 4-methyl-1-pentene copolymer composition (X)] <Content of constituent units> The quantification of 4-methyl-1-pentene and α-olefin content in the polymer is performed using the following apparatus and conditions. 13 The results are based on measurements using 1C-NMR. However, the α-olefin content in these measurements does not include the content of 4-methyl-1-pentene.

[0120] Using a nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd., model number: ECP500), the following measurements were taken: orthodichlorobenzene / deuterated benzene (80 / 20 vol%) mixed solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120°C, and the observed nucleus was 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 times, with 27.50 ppm as the reference value for chemical shift. 13 The composition of the 4-methyl-1-pentene polymer (A) was quantified by 13C-NMR spectroscopy. <Intrinsic viscosity> The intrinsic viscosity was measured using an Ubbelohde viscometer at 135°C in decalin. Approximately 20 mg of the polymerization powder, pellets, or resin lumps obtained below were taken and dissolved in 15 mL of decalin. The specific viscosity ηsp of the resulting decalin solution was measured in an oil bath heated to 135°C. After diluting this decalin solution by adding 5 mL of decalin, the specific viscosity ηsp was measured under the same conditions. This dilution procedure was repeated two more times, and the intrinsic viscosity [η] was calculated as the ηsp / C value when the polymer concentration (C) was extrapolated to zero (see the formula below).

[0121] [η] = lim(ηsp / C) (C→0) <Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn)> Molecular weight was measured by gel permeation chromatography (GPC).

[0122] Specifically, a Waters ALC / GPC150-Cplus liquid chromatograph (integrated differential refractometer detector) was used, with two GMH6-HT columns and two GMH6-HTL columns connected in series from Tosoh Corporation used as separation columns, o-dichlorobenzene as the mobile phase medium, and 0.025% by mass of dibutylhydroxytoluene (Takeda Pharmaceutical Company Limited) as an antioxidant. The mobile phase medium was moved at 1.0 mL / min, the sample concentration was 15 mg / 10 mL, the sample injection volume was 500 μL, and a differential refractometer was used as the detector. Standard polystyrene used was standard polystyrene from Tosoh Corporation with a weight-average molecular weight (Mw) of 1,000 to 4,000,000.

[0123] The obtained chromatograms were analyzed by creating calibration curves using standard polystyrene samples using known methods to calculate the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn value). The measurement time per sample was 60 minutes. <Melting point (Tm)> The melting point (Tm) of the polymer was measured using differential scanning calorimeter (PerkinElmer, model number: DSC8500) by DSC measurement.

[0124] Specifically, 7-12 mg of the polymer obtained in the synthesis example below was sealed in an aluminum pan and heated from room temperature to 200°C at a rate of 10°C / min. Then, to completely melt the polymer, it was held at 250°C for 5 minutes, and subsequently cooled to -50°C at a rate of 10°C / min. After being left at -50°C for 5 minutes, the sample was heated again to 250°C at a rate of 10°C / min. The peak temperature during this second heating was adopted as the melting point (Tm). <density> The measurements were taken using a density gradient tube in accordance with JIS K7112 (1999). <Melt Flow Rate (MFR)> The 4-methyl-1-pentene polymer (A) was measured according to ASTM D1238 at a temperature of 260°C and a load of 5.0 kgf (49.03 N). The 4-methyl-1-pentene polymer (B) was measured according to ASTM D1238 at a temperature of 230°C and a load of 2.16 kgf (21.18 N). <Manufacturing of molded products> Using a 4-methyl-1-pentene copolymer composition (X), a rectangular plate measuring 120 mm in length, 130 mm in width, and 2.0 mm in thickness was fabricated using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., model number: ES75SXIII, clamping force 735 kN, screw diameter Φ32 mm), as well as a dumbbell-shaped test specimen with a thickness of 3.2 mm conforming to ASTM D638 Type IV, a bending test specimen with a thickness of 3.2 mm conforming to ASTM D790, and an Izod test specimen with a thickness of 6.0 mm conforming to ASTM D256 for mechanical property measurement. The main molding conditions are as follows.

[0125] • Cylinder temperature setting: 220~240℃ • Screw rotation speed: 100 rpm • Injection pressure: 30-40 MPa ·Injection speed: 25~30mm / sec • Mold temperature: 30-60℃ ·Cooling time: 30~60 seconds <Mechanical properties: Tensile breaking strength, tensile elongation, and flexural modulus> The physical properties of the molded body were measured using the test specimens prepared as described above, by the following method.

[0126] The tensile breaking strength and tensile elongation of the molded article were measured by tensile testing using the dumbbell-shaped test specimens described above. The tensile tests were performed using a five-strand tensile testing machine (manufactured by Intesco Co., Ltd., model number: 2005X-5) at 23°C in accordance with ASTM D638, at a test speed of 50 mm / min.

[0127] The flexural modulus was tested using a 3.2 mm thick specimen. The test was conducted using a 5-span bending tester (Shimadzu Corporation, model number: AG-1kNX plus) at 23°C in accordance with ASTM D790, with a span distance of 51 mm and a test speed of 1.3 mm / min.

[0128] A higher tensile elongation value indicates superior toughness and flexibility at room temperature. Conversely, higher tensile strength and flexural modulus values ​​indicate superior rigidity. <Toughness: Izod impact test> A notch (cut) was made on one side of a 6.0 mm thick Izod test specimen obtained by the method described above using a cutter. At 23°C and -15°C, the test specimen was struck with a hammer from the direction of the notch under conditions of a hammer capacity of 3.92 J and a swing angle of 148.9°. The fracture and non-fracture status of the test specimen was observed, and the impact value (J / m) when the test specimen fractured was measured. The Izod impact test was performed on each of the five test specimens, and the average of the obtained impact values ​​was calculated for evaluation. A higher impact value indicates better toughness (fracture resistance). If some of the five test specimens fractured (i.e., none of the five test specimens fractured), the impact value of only the fractured test specimens was used to calculate the average and perform the evaluation. <Dynamic viscoelasticity> Test specimens measuring 35 mm in length and 10 mm in width were prepared by punching out a 2.0 mm thick rectangular plate molded body obtained by the method described above. Using a rheometer (Anton Paar, model number: MCR301), under the conditions of torsion mode, frequency 10 rad / s (1.6 Hz), strain setting 0.1%, and heating rate 2 °C / min, the tanδ peak temperature in the temperature range of 0 to 240 °C and the tanδ peak value in the temperature range of 0 to 100 °C were observed for the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer composition (X). Under similar measurement conditions, the tanδ peak temperature and tanδ peak value were observed for the 4-methyl-1-pentene polymer (B) in the temperature range of -40 to 150 °C. <Shape retention: Dimensional change rate (molding shrinkage rate)> The shrinkage rate was calculated using the dimensional change according to the following formula, after measuring the length (of all four sides) of the 2.0 mm thick square plate molded as described above and obtaining the average value.

[0129] Dimensional change rate (%) = [(Length of injection mold - Length of molded square plate) / (Length of injection mold)] × 100 A smaller dimensional change rate indicates better shape retention performance at high temperatures. <Release properties (critical surface tension)> To evaluate the critical surface tension, a 2.0 mm thick rectangular plate molded body obtained by the method described above was cut to dimensions of 75 mm in length and 75 mm in width, and one of these pieces was used as a test specimen. Wetting tension test mixtures of ethylene glycol monoethyl ether / formamide, adjusted to surface tensions of 31 mN / m, 34 mN / m, 37 mN / m, and 40 mN / m, respectively (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), were dropped onto the surface of the test specimen under an atmosphere of 23°C and 50% relative humidity. Then, the contact angle of each tension test mixture on the test specimen was measured using an image processing type solid-liquid interface analysis system (manufactured by Kyowa Interface Science Co., Ltd., model number: DropMaster500).

[0130] Using the Zisman plotting method, the surface tension values ​​of the tensile test mixtures were plotted on the x-axis, and the measured contact angle (converted to radians and defined as cosθ) was plotted on the y-axis. A linear function was obtained using the least squares method. This linear function was extrapolated to cosθ = 1.0, which is considered to be the completely wetted state, and the intersection point with the x-axis was calculated as the critical surface tension (mN / m). A smaller value of critical surface tension (mN / m) indicates better mold release properties. <Pull-out properties> Using a 30mmφ single-screw extruder, strands of the 4-methyl-1-pentene polymerization composition (X) were collected using a circular die (5.0mmφ). An unvulcanized rubber composition (0.5mm thick) was wrapped around the strands, and then both were heated at 160°C for 60 minutes to vulcanize them into a rubber hose. After cooling to 23°C, an air gun connected to compressed air was inserted into the end, and the mandrel was pulled out from the vulcanized rubber hose-shaped body by pushing it out with compressed air from the end, simulating the process.

[0131] In this test, if the material could be removed with a single air injection, it was judged to have excellent extraction properties and was rated "A". If it could be removed with several air injections, it was rated "B", and if it could not be removed, it was rated "C". The results are shown in Table 2. [Production of 4-methyl-1-pentene polymers (A-1) and (A-2)] Polymers (A-1) and (A-2) having the properties shown in Table 1 were obtained by changing the proportions of 4-methyl-1-pentene, 1-decene, 1-hexadecene, 1-octadecene, and hydrogen, in accordance with the polymerization methods described in Comparative Examples 7 and 9 of International Publication No. 2006 / 054613. [Synthesis of 4-methyl-1-pentene polymer (B)] <Synthesis example B-1> 750 mL of 4-methyl-1-pentene was charged into a 1.5-liter stainless steel autoclave with stirring blades, which had been thoroughly purged with nitrogen, at 23°C. 0.75 mL of a 1.0 mmol / mL toluene solution of triisobutylaluminum (TIBAL) was then charged into the autoclave, and the mixture was stirred.

[0132] Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene to a total pressure of 0.13 MPa (gauge pressure). Subsequently, 0.34 mL of a toluene solution containing 1 mmol of pre-prepared methylaluminoxane (in terms of Al) and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride was injected into the autoclave under nitrogen pressure to start polymerization. During the polymerization reaction, the temperature inside the autoclave was adjusted to 60°C. 60 minutes after the start of polymerization, 5 mL of methanol was injected into the autoclave under nitrogen pressure to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Then, acetone was added to the reaction solution while stirring.

[0133] The resulting polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours. The amount of polymer (B-1) obtained was 36.9 g, with a content of 72.5 mol% of constituent unit (i) and 27.5 mol% of constituent unit (ii). The physical properties of the obtained polymer (B-1) are shown in Table 1. <Synthesis example B-2> A 1.5-liter stainless steel autoclave with a stirring blade, thoroughly purged with nitrogen, was charged with 300 mL of n-hexane (dried in a dry nitrogen atmosphere with activated alumina) and 450 mL of 4-methyl-1-pentene at 23°C. 0.75 mL of a 1.0 mmol / mL toluene solution of triisobutylaluminum (TIBAL) was then added to the autoclave, and the stirrer was turned on.

[0134] Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene to a total pressure of 0.19 MPa (gauge pressure). Subsequently, 0.34 mL of a toluene solution containing 1 mmol of pre-prepared methylaluminoxane (in terms of Al) and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride was injected into the autoclave under nitrogen pressure to start polymerization. During the polymerization reaction, the temperature inside the autoclave was adjusted to 60°C. 60 minutes after the start of polymerization, 5 mL of methanol was injected into the autoclave under nitrogen pressure to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Then, acetone was added to the reaction solution while stirring.

[0135] The resulting polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours. The amount of polymer (B-2) obtained was 44.0 g, with a content of 84.1 mol% for constituent unit (i) and 15.9 mol% for constituent unit (ii). The physical properties of the obtained polymer (B-2) are shown in Table 1.

[0136] In Table 1, "Type of α-olefin" refers to the type of α-olefin other than 4-methyl-1-pentene. Furthermore, "Constituent unit derived from α-olefin (ii)" refers to a constituent unit derived from ethylene and at least one selected from α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), and "Constituent unit derived from α-olefin (iii)" refers to a constituent unit derived from ethylene and at least one selected from α-olefins having 10 to 20 carbon atoms.

[0137] [Table 1] [Thermoplastic elastomer (C)] The following thermoplastic elastomer (C) was used. • Olefin-based thermoplastic elastomer (C-1-1): Manufactured by ExxonMobil Chemicals, Product name: Vistamaxx (registered trademark) 6202 (MFR (230℃, load 2.16kgf (21.18N)) = 20g / 10min, Tm (melting point) = 110℃) • Styrene-based thermoplastic elastomer (C-2-1): Manufactured by Asahi Kasei Corporation. Product name: ToughTec (registered trademark) H-1052 (MFR (230℃, load 2.16kgf (21.18N)) = 13g / 10min, Tm (melting point) not observed). • Olefin-based thermoplastic elastomer (C-1-2): Manufactured by Mitsui Chemicals, Inc. Product name: Toughmer (registered trademark) PN-2060 (MFR (230℃, load 2.16kgf (21.18N)) = 6.0g / 10min, Tm (melting point) = 160℃) [Example 1] A resin composition containing 80 parts by mass of 4-methyl-1-pentene polymer (A-1), 10 parts by mass of 4-methyl-1-pentene polymer (B-1), and 10 parts by mass of thermoplastic elastomer (C-1-1) was melt-kneaded according to the method described above to obtain pellets. Then, molded articles and various test pieces were prepared using these pellets according to the method described above, and the physical properties were evaluated as described above. The results are shown in Table 2. [Example 2] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 70 parts by mass of 4-methyl-1-pentene polymer (A-1), 20 parts by mass of 4-methyl-1-pentene polymer (B-1), and 10 parts by mass of thermoplastic elastomer (C-1-1), and the physical properties described above were evaluated. The results are shown in Table 2. [Example 3] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 60 parts by mass of 4-methyl-1-pentene polymer (A-1), 20 parts by mass of 4-methyl-1-pentene polymer (B-1), and 20 parts by mass of thermoplastic elastomer (C-1-1), and the physical properties described above were evaluated. The results are shown in Table 2. [Example 4] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 70 parts by mass of 4-methyl-1-pentene polymer (A-1), 10 parts by mass of 4-methyl-1-pentene polymer (B-2), and 20 parts by mass of thermoplastic elastomer (C-1-1), and the physical properties described above were evaluated. The results are shown in Table 2. [Example 5] Pellets and test pieces were prepared using the same method as in Example 1, except that the resin composition contained 60 parts by mass of 4-methyl-1-pentene polymer (A-1), 20 parts by mass of 4-methyl-1-pentene polymer (B-2), and 20 parts by mass of thermoplastic elastomer (C-1-1). The physical properties described above were then evaluated. The results are shown in Table 2. [Example 6] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 60 parts by mass of 4-methyl-1-pentene polymer (A-2), 20 parts by mass of 4-methyl-1-pentene polymer (B-1), and 20 parts by mass of thermoplastic elastomer (C-1-1), and the physical properties described above were evaluated. The results are shown in Table 2. [Example 7] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 60 parts by mass of 4-methyl-1-pentene polymer (A-2), 20 parts by mass of 4-methyl-1-pentene polymer (B-2), and 20 parts by mass of thermoplastic elastomer (C-1-1), and the physical properties described above were evaluated. The results are shown in Table 2. [Example 8] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 60 parts by mass of 4-methyl-1-pentene polymer (A-1), 20 parts by mass of 4-methyl-1-pentene polymer (B-1), and 20 parts by mass of thermoplastic elastomer (C-1-2), and the physical properties described above were evaluated. The results are shown in Table 2. [Example 9] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 80 parts by mass of 4-methyl-1-pentene polymer (A-1), 10 parts by mass of 4-methyl-1-pentene polymer (B-1), and 10 parts by mass of thermoplastic elastomer (C-2-1), and the physical properties described above were evaluated. The results are shown in Table 2. [Comparative Example 1] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 100 parts by mass of 4-methyl-1-pentene polymer (A-1), and the physical properties described above were evaluated. The results are shown in Table 2. [Comparative Example 2] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 80 parts by mass of 4-methyl-1-pentene polymer (A-1) and 20 parts by mass of 4-methyl-1-pentene polymer (B-1), and the physical properties described above were evaluated. The results are shown in Table 2. [Comparative Example 3] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 80 parts by mass of 4-methyl-1-pentene polymer (A-1) and 20 parts by mass of thermoplastic elastomer (C-1-1), and the physical properties described above were evaluated. The results are shown in Table 2. [Comparative Example 4] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 60 parts by mass of 4-methyl-1-pentene polymer (A-1) and 40 parts by mass of thermoplastic elastomer (C-1-2), and the physical properties described above were evaluated. The results are shown in Table 2. [Comparative Example 5] Pellets and various test pieces were prepared using the same method as in Example 1, except that the resin composition contained 25 parts by mass of 4-methyl-1-pentene polymer (A-1) and 75 parts by mass of 4-methyl-1-pentene polymer (B-1), and the physical properties described above were evaluated. The results are shown in Table 2.

[0138] [Table 2] In Table 2, "-" indicates that the corresponding ingredient is not present.

[0139] The molded article made from the 4-methyl-1-pentene copolymer composition (X) according to the present invention can maintain its shape at high temperatures, and the resulting molded article exhibits excellent toughness at low temperatures. Furthermore, the molded article made from the 4-methyl-1-pentene copolymer composition (X) according to the present invention maintains the heat resistance of the 4-methyl-1-pentene polymer (A) while improving flexibility and toughness at low temperatures. For example, even when the mandrel is rapidly withdrawn from the rubber hose manufactured using a mandrel, sufficient release properties can be obtained without deformation.

Claims

1. 50 to 90 parts by mass of a 4-methyl-1-pentene polymer (A) whose melting point is measured by differential scanning calorimetry (DSC) in the range of 200 to 250°C, 5 to 30 parts by mass of a 4-methyl-1-pentene polymer (B) whose melting point is less than 200°C as measured by differential scanning calorimetry (DSC), or in which no melting point is observed, The thermoplastic elastomer (C) other than the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene polymer (B) comprises 5 to 30 parts by mass (the total amount of (A), (B), and (C) being 100 parts by mass), The 4-methyl-1-pentene polymer (A) satisfies the following requirement (c): The 4-methyl-1-pentene polymer (B) satisfies the following requirement (f): The thermoplastic elastomer (C) is an olefin-based elastomer (C-1) or a styrene-based elastomer (C-2), The olefin-based elastomer (C-1) is a copolymer of one selected from the group consisting of ethylene and propylene, and at least one selected from the group consisting of butadiene, hydrogenated butadiene, isoprene, hydrogenated isopreneisobutylene, and α-olefin, and A 4-methyl-1-pentene copolymer composition (X) that satisfies the following requirements (a) and (b); Requirement (a): The temperature at which the loss tangent tanδ, determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz), is maximum is between 0°C and 60°C within the temperature range of 0°C to 240°C; Requirement (b): The value of the loss tangent tanδ obtained by dynamic viscoelastic measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of 0 to 100°C is 0.15 to 0.8; Requirement (c): The amount of constituent units derived from 4-methyl-1-pentene is 93.2 to 92 mol%, and the amount of constituent units derived from at least one selected from the group consisting of ethylene and α-olefins having 10 to 20 carbon atoms is in the range of 6.8 to 8 mol% [provided that the total amount of constituent units derived from 4-methyl-1-pentene and constituent units derived from ethylene and α-olefins having 10 to 20 carbon atoms is 100 mol%]; Requirement (f): Consists of 68 to 72.5 mol% of constituent unit (i) derived from 4-methyl-1-pentene and 27.5 to 32 mol% of constituent unit (ii) derived from ethylene and at least one α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (provided that the total of constituent unit (i) and constituent unit (ii) is 100 mol%).

2. A 4-methyl-1-pentene copolymer composition (X) according to claim 1, wherein the 4-methyl-1-pentene polymer (A) satisfies requirement (d) below, and the 4-methyl-1-pentene polymer (B) satisfies requirements (g) and (h) below; Requirement (d): Density of 820-850 kg / m³ ３ Within the range; Requirement (g): The tanδ peak temperature, determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of -40 to 150°C, is between 15°C and 45°C; Requirements (h): Density of 830-870 kg / m³ ３ It is within the range.

3. A molded article formed from the 4-methyl-1-pentene copolymer composition (X) described in claim 1.

4. A mandrel formed from the 4-methyl-1-pentene copolymer composition (X) according to claim 1 or claim 2.

5. A step of obtaining a mandrel by extruding the 4-methyl-1-pentene copolymer composition (X) according to claim 1 or claim 2, A step of manufacturing a rubber hose using the mandrel obtained in the above step, A method for manufacturing rubber hoses, including the method described above.

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