Polymer composition and molded product

Abstract

To provide a polymer composition capable of providing a molded product which has excellent transparency even when subjected to high pressure steam sterilization and having excellent moldability when blow molded.SOLUTION: Provided are: a polymer composition that comprises: a 4-methyl-1-pentene-based polymer and satisfies the following requirements (1) and (2); and a molded product comprising the composition: (1) the cumulative elution amount in temperature rising elution fractionation up to 20°C is 4.0 mass% or more; and (2) the value obtained by subtracting the value of the cumulative elution amount in temperature rising elution fractionation up to 20°C from the value of the cumulative elution amount in temperature rising elution fractionation up to 100°C is 4.0 mass% or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer composition and a molded article. [Background technology]

[0002] 4-methyl-1-pentene polymers, such as 4-methyl-1-pentene homopolymers and 4-methyl-1-pentene copolymers, are resins that have superior properties compared to polyethylene and polypropylene, such as heat resistance, transparency, light weight, mold releasability, gas permeability, and electrical properties, and are used in a variety of fields, including food containers, secondary materials for electronic and information components, laboratory equipment, stationery, crosslinking process materials, release films, films for electronic and information components, food packaging materials, and synthetic paper.

[0003] As an example of such a 4-methyl-1-pentene polymer, a 4-methyl-1-pentene polymer having high stereoregularity and a large heat of fusion is disclosed in Patent Document 1. Furthermore, for example, Patent Document 2 discloses a molded article made of a resin composition containing a 4-methyl-1-pentene polymer that utilizes the properties of the polymer and has improved shape retention and stain resistance at high temperatures. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2014 / 050817 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-183141 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when the 4-methyl-1-pentene polymers described in Patent Documents 1 and 2 and molded articles made of the polymers are subjected to sterilization using water vapor, i.e., high-pressure steam sterilization (autoclave sterilization: AC sterilization), cloudiness may occur, and there is room for improvement in the transparency of the molded articles after high-pressure steam sterilization.

[0006] The problem to be solved by one embodiment of the present invention is to provide a polymer composition from which a molded article having excellent transparency can be obtained even when subjected to high-pressure steam sterilization, and which has excellent moldability during blow molding. The problem to be solved by another embodiment of the present invention is to provide a molded article having excellent transparency even when subjected to high-pressure steam sterilization, and which has excellent moldability during blow molding. [Means for solving the problem]

[0007] As a result of further investigations, the present inventors have found that the above-mentioned problems can be solved by a polymer composition containing a 4-methyl-1-pentene polymer that satisfies specific requirements, and have thus completed the present invention.

[0008] The means for solving the above problems include the following aspects. <1> Contains a 4-methyl-1-pentene polymer, A polymer composition that satisfies the following requirements (1) and (2): (1) The cumulative elution amount up to 20°C in temperature-rising elution fractionation is 4.0% by mass or more; (2) In temperature rising elution fractionation, the value obtained by subtracting the cumulative elution amount up to 20°C from the cumulative elution amount up to 100°C is 4.0 mass% or more. <2> the maximum value of the mass fraction per unit temperature (dW / dT) in the elution temperature range of 40°C to 80°C in temperature rising elution fractionation is 2.00 mass% / °C or less; The minimum value of the mass fraction per unit temperature (dW / dT) in the elution temperature range of 40°C to 80°C in temperature rising elution fractionation is 0.10 mass% / °C or more; <1> The polymer composition according to claim 1. <3> The cumulative elution amount up to 100 ° C. in temperature rising elution fractionation is 42.0 to 62.0 mass%; <1> or <2> The polymer composition according to claim 1. <4> The 4-methyl-1-pentene polymer is 0.5 to 30 mass% of a 4-methyl-1-pentene polymer (A) satisfying the following requirement (Ai); 0.5 to 30 mass% of a 4-methyl-1-pentene copolymer (B) satisfying the following requirement (Bi); and 40 to 99 mass% of a 4-methyl-1-pentene copolymer (C) satisfying the following requirement (Ci) (where the total content of the polymer (A), the copolymer (B), and the copolymer (C) is taken as 100 mass%), <1> ~ <3> 1. The polymer composition according to any one of the preceding claims. (Ai) When the total of the structural units (i) derived from 4-methyl-1-pentene and the structural units (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is taken as 100 mol%, the content of the structural units (i) is more than 98.0 mol% and 100 mol% or less, and the content of the structural units (ii) is 0 mol% or more and less than 2.0 mol%; (Bi) When the total of the structural units (i) derived from 4-methyl-1-pentene and the structural units (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is taken as 100 mol %, the content of the structural units (i) is 90.0 mol % or less, and the content of the structural units (ii) is 10.0 mol % or more; (Ci) When the total of the structural units (i) derived from 4-methyl-1-pentene and the structural units (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is taken as 100 mol %, the content of structural units (i) is more than 90.0 mol % and 98.0 mol % or less, and the content of structural units (ii) is 2.0 mol % or more and less than 10.0 mol %. <5> The polymer (A), the copolymer (B), and the copolymer (C) each have an intrinsic viscosity in decalin at 135°C of 1.0 to 5.0 dL / g. <4> The polymer composition according to claim 1. <6> The melting point of the polymer (A) is 200 to 250°C, The melting point of the copolymer (B) is 200°C or less, or no melting point is observed, The melting point of the copolymer (C) is 200 to 250°C. <4> or <5> The polymer composition according to claim 1. <7> <1> ~ <6> A molded article comprising the polymer composition according to any one of the above items. <8> It is a bottle container, <7> The molded article according to claim 1. <9> It is a baby bottle, <7> The molded article according to claim 1. [Effects of the Invention]

[0009] According to one embodiment of the present invention, there is provided a polymer composition which gives a molded article which has excellent transparency even when subjected to high-pressure steam sterilization and which has excellent moldability during blow molding. Also, according to one embodiment of the present invention, there is provided a molded article which has excellent transparency even when subjected to high-pressure steam sterilization and which has excellent moldability during blow molding. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, unless otherwise specified, for example, when referring to the numbers α and β, the expression α to β means α or more and β or less. In this specification, polymerization and copolymerization may be collectively referred to as polymerization. Furthermore, 4-methyl-1-pentene homopolymers and 4-methyl-1-pentene copolymers may be collectively referred to as 4-methyl-1-pentene polymers or simply as "polymers." Furthermore, the various monomers used in the composition of the present invention may be derived from fossil raw materials, may be derived from living organisms such as biomass, or may be a mixture of these.

[0011] <Polymer composition> The polymer composition of the present invention contains a 4-methyl-1-pentene polymer and satisfies the requirements (1) and (2). The components of the polymer composition of the present invention will be described in detail below.

[0012] <<Requirement (1)>> (1) The cumulative elution amount up to 20°C in temperature rising elution fractionation (hereinafter, sometimes referred to as "TREF") is 4.0% by mass or more. When the polymer composition has a cumulative elution amount of 4.0% by mass or more up to 20°C in temperature-rising elution fractionation, the polymer composition contains a large amount of low-crystalline components, resulting in good moldability. When the cumulative elution amount up to 20°C is less than 4.0% by mass, the polymer composition is likely to contain insufficient low-crystalline components, resulting in molding defects during blow molding. From the viewpoint of superior moldability, the polymer composition of the present invention preferably has a cumulative elution amount up to 20° C. in TREF of 5.0 to 30.0 mass %, more preferably 6.0 to 24.0 mass %.

[0013] The cumulative elution amount up to 20°C in TREF can be adjusted by the content of low-crystalline components (e.g., amorphous components) in the resin components contained in the polymer composition. In addition, when the polymer composition contains the 4-methyl-1-pentene polymer (A) and 4-methyl-1-pentene copolymers (B) and (C) described below, the cumulative elution amount can also be adjusted by the content of these polymers or the content of the structural units (i) and (ii) contained therein. The temperature rising elution fractionation and cumulative elution amount can be determined by the methods described in the Examples below.

[0014] <<Requirement (2)>> The value obtained by subtracting the cumulative elution amount up to 20°C from the cumulative elution amount up to 100°C in temperature rising elution fractionation (TREF) is 4.0 mass% or more. The inventors presume that if this value is 4.0% by mass or more, components with different crystallinity levels are mixed in the polymer composition, making it difficult for the low-crystalline component to aggregate, and water aggregation is also difficult to occur, so that even when high-pressure steam sterilization is performed, cloudiness is unlikely to occur in the polymer, resulting in excellent transparency. On the other hand, the inventors presume that if this value is less than 4.0% by mass, the crystalline component is likely to localize, and water aggregates in the localized parts of the crystalline component when high-pressure steam sterilization is performed, causing cloudiness in the molded product. The value obtained by subtracting the cumulative elution amount up to 20°C from the cumulative elution amount up to 100°C in temperature rising elution fractionation is preferably 10.0 to 60.0 mass%, more preferably 20.0 to 55.0 mass%, from the viewpoint of transparency when high-pressure steam sterilization is performed.

[0015] The polymer composition may satisfy the following requirements (3) and / or (4). <<Requirement (3)>> The cumulative amount of elution up to 100° C. in TREF is preferably 42.0 to 62.0 mass %, more preferably 45.0 to 60.0 mass %. The cumulative amount of elution up to 100°C in TREF can be adjusted by the content of highly crystalline components in the components contained in the composition. When the composition contains the 4-methyl-1-pentene polymer (A) and 4-methyl-1-pentene copolymers (B) and (C) described below, the cumulative amount of elution can also be adjusted by the content of these polymers and the content of structural units (i) and (ii) contained therein.

[0016] <<Requirement (4)>> The cumulative elution amount in TREF at 0° C. is preferably 0.5 to 5.0% by mass, and more preferably 1.0 to 4.0% by mass. The cumulative amount of elution up to 100°C in TREF can be adjusted by the content of highly crystalline components in the components contained in the polymer composition. When the polymer composition contains the 4-methyl-1-pentene polymer (A) and 4-methyl-1-pentene copolymers (B) and (C) described below, the cumulative amount of elution can also be adjusted by the content of these polymers and the content of structural units (i) and (ii) contained therein.

[0017] The maximum value of the mass fraction per unit temperature (dW / dT) in the elution temperature range of 40°C to 80°C in TREF is preferably 2.00 mass% / °C or less, more preferably 0.50 to 1.00 mass% / °C. When the maximum value of dW / dT is within the above range, resin components with different crystallinity are mixed in the composition, making it difficult for the low-crystalline component to aggregate and water to aggregate, so that even when subjected to high-pressure steam sterilization, the molded product is less likely to become cloudy and has excellent transparency, which is preferable. The maximum value of dW / dT in TREF can be adjusted by the content ratio of the high-crystalline component and the low-crystalline component in the components contained in the composition, and when the composition contains the 4-methyl-1-pentene polymer (A) and 4-methyl-1-pentene copolymers (B) to (C) described below, it can also be adjusted by the contents of these and the contents of the structural units (i) and (ii) contained therein.

[0018] In TREF, the minimum value of the mass fraction per unit temperature (dW / dT) of the polymer composition of the present invention in the elution temperature range of 40°C to 80°C is preferably 0.10 mass% / °C or more, and more preferably 0.15 mass% / °C or more and less than 0.50 mass% / °C. When the minimum value of dW / dT is within the above range, components with different crystallinity are mixed in the composition, so that the low-crystalline component is less likely to aggregate, and water is also less likely to aggregate, so that cloudiness is less likely to occur even when high-pressure steam sterilization is performed, resulting in excellent transparency, which is preferable. The minimum value of dW / dT in the TREF of the polymer composition of the present invention can be adjusted by the content ratio of the high-crystalline component to the low-crystalline component in the components contained in the composition, and when the composition contains the 4-methyl-1-pentene polymer (A) and 4-methyl-1-pentene copolymers (B) to (C) described below, it can also be adjusted by the contents of these and the contents of the structural units (i) and (ii) contained therein. From the viewpoint of achieving excellent transparency and preventing cloudiness even when the molded body is subjected to high-pressure steam sterilization, the mass fraction per unit temperature (dW / dT) in the elution temperature range of 40°C to 80°C in temperature rising elution fractionation is preferably 0.10 to 2.00 mass% / °C, more preferably 0.15 to 1.00 mass% / °C, even more preferably 0.20 to 1.00 mass% / °C, and particularly preferably 0.26 to 1.00 mass% / °C.

[0019] The polymer composition is not particularly limited as long as it satisfies the above requirements (1) and (2) and contains a 4-methyl-1-pentene polymer. As the 4-methyl-1-pentene polymer, the polymer composition preferably contains the following 4-methyl-1-pentene polymer (A), 4-methyl-1-pentene copolymer (B), and 4-methyl-1-pentene copolymer (C).

[0020] <4-methyl-1-pentene polymer (A)> The 4-methyl-1-pentene polymer (A) (hereinafter also referred to as "polymer (A)") preferably satisfies one or more of the following requirements (Ai) to (A-iii), more preferably the polymer (A) satisfies the requirements (Ai) and (A-ii), and even more preferably the polymer (A) satisfies all of the requirements (Ai) to (A-iii).

[0021] The polymer (A) may contain only one type of polymer, or may contain two or more types of polymers. When the polymer (A) contains two or more types of polymers, it is preferable that each of the contained polymers satisfies one or more of the following requirements (Ai) to (A-iii).

[0022] <<Requirements (Ai)>> When the total content of the structural unit (i) derived from 4-methyl-1-pentene and the content of the structural unit (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is taken as 100 mol%, the content of the structural unit (i) is preferably more than 98.0 mol% and 100 mol% or less, and the content of the structural unit (ii) is preferably at least 0 mol% and less than 2.0 mol%.

[0023] In the polymer (A), when the total content of the structural unit (i) and the content of the structural unit (ii) is taken as 100 mol %, the content of the structural unit (i) derived from 4-methyl-1-pentene is more preferably 98.5 to 99.5 mol %. Furthermore, when the total content of the structural unit (i) and the content of the structural unit (ii) is taken as 100 mol %, the content of the structural unit (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more preferably 0.5 to 1.5 mol %.

[0024] In the polymer (A), when the content of the structural unit (i) derived from 4-methyl-1-pentene and the content of the structural unit (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) are within the above ranges, a polymer composition with good moldability while maintaining heat resistance can be obtained.

[0025] Examples of the monomer that derives the structural unit (ii) contained in the polymer (A) include ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene). Examples of such monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene. Among these, from the viewpoint of heat resistance, the monomer from which structural unit (ii) is derived is preferably a linear α-olefin having 6 to 18 carbon atoms, and more preferably a linear α-olefin having 10 to 18 carbon atoms. Specific examples of linear α-olefins having 10 to 18 carbon atoms include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, and 1-octadecene, with 1-decene, 1-hexadecene, and 1-octadecene being particularly preferred.

[0026] The α-olefin from which the structural unit (ii) contained in the polymer (A) is derived may be one type, or two or more types.

[0027] The polymer (A) may further contain structural units derived from 4-methyl-1-pentene and other polymerizable compounds other than ethylene and α-olefins having 3 to 20 carbon atoms, provided that the object of the present invention is not impaired. Other polymerizable compounds include, for example, vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids or derivatives thereof such as maleic anhydride; conjugated dienes such as butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; Examples of non-conjugated polyenes include dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene.

[0028] In polymer (A), the content of structural units derived from other polymerizable compounds is usually 10 mol % or less, preferably 5 mol % or less, and more preferably 3 mol % or less, relative to 100 mol % of all structural units constituting polymer (A).

[0029] <<Requirement (A-ii)>> Intrinsic viscosity [η] of polymer (A) measured in decalin at 135°C A is preferably 1.0 to 5.0 dl / g, more preferably 1.5 to 4.0 dl / g, and even more preferably 2.0 to 3.0 dl / g. A can be adjusted, for example, by the amount of hydrogen added in the polymerization step when producing the polymer (A).

[0030] [η] A The polymer (A) having [η] in the above range exhibits good fluidity during preparation of the polymer composition and during molding. AWhen the amount is within the above range, when combined with the 4-methyl-1-pentene copolymer (B) and the 4-methyl-1-pentene copolymer (C) described later, they are likely to be melt-kneaded uniformly, and the resulting molded article will have excellent transparency and will contribute to improved blow moldability.

[0031] <<Requirements (A-iii)>> The melting point (Tm) measured by a differential scanning calorimeter (DSC) according to the method described in the examples below is preferably 200 to 250° C., more preferably 210 to 245° C., and even more preferably 220 to 240° C. When the melting point (Tm) measured by a differential scanning calorimeter (DSC) is within the above range, the polymer composition containing the polymer (A) and the molded article obtained from the polymer composition have good heat resistance. The melting point (Tm) value tends to depend on the stereoregularity of the polymer (A) and the content of the structural unit (ii) in the polymer (A). For this reason, the melting point (Tm) can be adjusted by using an olefin polymerization catalyst described below and further controlling the content of the structural unit (ii).

[0032] <4-methyl-1-pentene copolymer (B)> The 4-methyl-1-pentene copolymer (B) (hereinafter also referred to as "copolymer (B)") preferably satisfies one or more of the following requirements (Bi) to (B-iii). More preferably, the copolymer (B) satisfies all of the requirements (Bi) to (B-iii).

[0033] Copolymer (B) may contain only one type of copolymer, or may contain two or more types of copolymers. When copolymer (B) contains two or more types of copolymers, it is preferable that each of the copolymers contained satisfies one or more of the following requirements (Bi) to (B-iii):

[0034] <<Requirement (Bi)>> When the total of the content of structural units (i) derived from 4-methyl-1-pentene and the content of structural units (ii) derived from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is taken as 100 mol %, the content of structural units (i) is preferably 90.0 mol % or less, and the content of structural units (ii) is preferably 10.0 mol % or more.

[0035] In copolymer (B), when the total content of structural unit (i) and the content of structural unit (ii) is taken as 100 mol %, the content of structural unit (i) derived from 4-methyl-1-pentene is more preferably 60.0 to 87.5 mol %, and even more preferably 70.0 to 85.0 mol %. Furthermore, when the total content of the structural unit (i) and the content of the structural unit (ii) is taken as 100 mol %, the content of the structural unit (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more preferably 12.5 to 40.0 mol %, and even more preferably 15.0 to 30.0 mol %.

[0036] In the copolymer (B), when the content of the structural unit (i) derived from 4-methyl-1-pentene and the content of the structural unit (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) are within the above ranges, a polymer composition with good moldability can be obtained.

[0037] The α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) from which the structural unit (ii) contained in the copolymer (B) is derived is synonymous with the α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) from which the structural unit (ii) contained in the polymer (A) is derived, and the preferred embodiments are the same as those of the α-olefin. The α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) from which the structural unit (ii) contained in the copolymer (B) is derived may be one type only, or two or more types.

[0038] <<Requirements (B-ii)>> Intrinsic viscosity [η] of copolymer (B) measured in decalin at 135°C B is preferably 1.0 to 5.0 dl / g, more preferably 1.5 to 4.0 dl / g, and even more preferably 2.0 to 3.0. B can be adjusted, for example, by the amount of hydrogen added in the polymerization step when producing the copolymer (B).

[0039] [η] B The copolymer (B) having [η] in the above range exhibits good fluidity during preparation and molding of the polymer composition. Furthermore, when it is combined with the above-mentioned 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (C) described later, it is thought to contribute to improving the stretchability. B When [η] is in the above range, the mixture is melt-kneaded uniformly, which can contribute to improving transparency. B When the value is equal to or more than the lower limit, the polymer composition has better stretchability when molded.

[0040] <<Requirements (B-iii)>> The melting point (Tm) measured by a differential scanning calorimeter (DSC) according to the method described in the examples below is preferably 200°C or lower, or no melting point is observed, more preferably no melting point is observed. When the melting point of copolymer (B) is 200°C or lower or no melting point is observed, the polymer composition containing copolymer (B) can be easily stretched, and the thickness distribution of a molded article formed from the polymer composition tends to be narrow. When the melting point (Tm) is not observed, or when the melting point (Tm) is observed, the value tends to depend on the stereoregularity of the copolymer (B) and the content of the structural unit (ii) in the copolymer (B). Therefore, by using an olefin polymerization catalyst described later and further controlling the content of the structural unit (ii), it is possible to prepare a copolymer (B) in which the melting point (Tm) is not observed, and the melting point (Tm) can be adjusted to a desired value.

[0041] <4-methyl-1-pentene copolymer (C)> The 4-methyl-1-pentene copolymer (C) (hereinafter also referred to as "copolymer (C)") preferably satisfies one or more of the following requirements (Ci) to (C-iii). More preferably, the copolymer (C) satisfies all of the requirements (Ci) to (C-iii).

[0042] Copolymer (C) may contain only one type of copolymer, or may contain two or more types of copolymers. When copolymer (C) contains two or more types of copolymers, it is preferable that each copolymer satisfies one or more of the following requirements (Ci) to (C-iii).

[0043] <<Requirements (Ci)>> It contains structural units (i) derived from 4-methyl-1-pentene, and when the total of the content of structural units (i) and the content of structural units (ii) derived from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is taken as 100 mol %, the content of structural units (i) is preferably more than 90.0 mol % and not more than 98.0 mol %, and the content of structural units (ii) is preferably at least 2.0 mol % and less than 10.0 mol %.

[0044] In the copolymer (C), the content of the structural unit (i) derived from 4-methyl-1-pentene is more preferably 93.0 to 97.8 mol %, and even more preferably 95.0 to 97.5 mol %. The content of the structural unit (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more preferably 2.2 to 7.0 mol %, and even more preferably 2.5 to 5.0 mol %.

[0045] In the copolymer (C), when the content of the structural unit (i) derived from 4-methyl-1-pentene and the content of the structural unit (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) are within the above ranges, a polymer composition with good moldability can be obtained while maintaining the properties of the 4-methyl-1-pentene polymer (e.g., heat resistance, transparency, etc.).

[0046] The α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) from which the structural unit (ii) contained in the copolymer (C) is derived is synonymous with the α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) from which the structural unit (ii) contained in the polymer (A) is derived, and is the same as the preferred α-olefin. The α-olefin from which the structural unit (ii) contained in the copolymer (C) is derived may be one type, or two or more types.

[0047] <<Requirements (C-ii)>> Intrinsic viscosity [η] of copolymer (C) measured in decalin at 135°C C is preferably 1.0 to 5.0 dl / g, more preferably 1.5 to 4.0 dl / g, and even more preferably 2.0 to 3.0 dl / g. C can be adjusted, for example, by the amount of hydrogen added in the polymerization step when producing the copolymer (C).

[0048] [η] C The copolymer (C) having [η] in the above range exhibits good fluidity during preparation and molding of the polymer composition. Furthermore, it is considered that when it is combined with the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B), it contributes to improving the stretchability. In particular, [η] C When is equal to or greater than the lower limit, the polymer composition (X) has better stretchability when molded.

[0049] <<Requirements (C-iii)>> The melting point (Tm) measured by a differential scanning calorimeter (DSC) according to the method described in the examples below is preferably 200 to 250° C., more preferably 210 to 245° C., and even more preferably 220 to 240° C. When the melting point (Tm) measured by a differential scanning calorimeter (DSC) is within the above range, the polymer composition containing the copolymer (C) and the molded article obtained from the polymer composition have good heat resistance. The melting point (Tm) value tends to depend on the stereoregularity of the copolymer (C) and the content of the structural unit (ii) in the copolymer (C). Therefore, the melting point (Tm) can be adjusted by using an olefin polymerization catalyst described below and further controlling the content of the structural unit (ii).

[0050] <Methods for producing polymer (A), copolymer (B), and copolymer (C)> Any of the polymer (A), copolymer (B), and copolymer (C) can be obtained by polymerizing 4-methyl-1-pentene, an olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) from which the structural unit (ii) described above is derived, and, if necessary, the other monomers described above, in the presence of an olefin polymerization catalyst, by a known method.

[0051] Examples of olefin polymerization catalysts that can be used in producing the polymer (A) and the copolymer (B) include metallocene catalysts. Preferred metallocene catalysts include those described in WO 01 / 53369, WO 01 / 27124, JP-A 3-193796, JP-A 02-41303, WO 06 / 025540, WO 2013 / 009876, WO 2014 / 050817, WO 2014 / 123212, or WO 2017 / 150265.

[0052] Both the polymer (A) and the copolymer (B) may be polymerized in the presence of another polymer by multi-stage polymerization. For example, the polymer (A) may be polymerized in the first polymerization stage, and the copolymer (B) may be polymerized in the presence of the polymer (A). Similarly, the polymer (A) may be polymerized in the presence of the copolymer (B), and the copolymer (B) may also be polymerized in the presence of the polymer (A).

[0053] Examples of olefin polymerization catalysts that can be used in producing the copolymer (C) include Ziegler-Natta catalysts, such as the solid titanium catalyst components described in WO 2006 / 054613.

[0054] As the polymer (A), the copolymer (B) and the copolymer (C), commercially available 4-methyl-1-pentene copolymers (for example, TPX (registered trademark) manufactured by Mitsui Chemicals, Inc.) may be used. The polymer (A) may be a polymer (A) prepared by heat-treating a 4-methyl-1-pentene polymer that has been produced using the catalyst, etc., in an extruder, a mixer, etc. Alternatively, the polymer (A) may be prepared by heat-treating a commercially available 4-methyl-1-pentene copolymer (for example, TPX (registered trademark) manufactured by Mitsui Chemicals, Inc.) in an extruder, a mixer, etc.

[0055] <Amounts of Various Components Blended in Polymer Composition> The content of polymer (A) (preferably polymer (A) satisfying requirement (Ai), more preferably polymer (A) satisfying all of requirements (Ai) to (A-iii)) in the polymer composition is preferably 0.5 to 30 mass%, more preferably 2 to 27 mass%, relative to 100 mass% of the total content of polymer (A), copolymer (B), and copolymer (C). The content of copolymer (B) (preferably polymer (B) satisfying requirement (Bi), more preferably polymer (B) satisfying all of requirements (Bi) to (B-iii)) in the polymer composition is preferably 0.5 to 30 mass%, more preferably 2 to 27 mass%, when the total content of polymer (A), copolymer (B), and copolymer (C) is taken as 100 mass%. The content of copolymer (C) (preferably polymer (C) satisfying requirement (Ci), more preferably polymer (C) satisfying all of requirements (Ci) to (C-iii)) in the polymer composition is preferably 40 to 99 mass%, more preferably 46 to 96 mass%, when the total content of polymer (A), copolymer (B), and copolymer (C) is taken as 100 mass%.

[0056] As described above, when a polymer composition contains polymer (A), copolymer (B), and copolymer (C) as 4-methyl-1-pentene polymers, copolymer (C) has the highest content among these polymers. Here, increasing the proportion of structural unit (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) in the polymer composition tends to more easily suppress crystallization when the polymer composition is cooled. Since copolymer (C) has a higher content of structural unit (ii) than polymer (A) and a higher content in polymer composition (X) than copolymer (B), the half-crystallization time of the polymer composition can be controlled by the content of copolymer (C). Appropriate control of the half-crystallization time of the polymer composition improves the blow moldability of the polymer composition. Furthermore, by setting the contents of polymer (A), copolymer (B), and copolymer (C) in the polymer composition within the above ranges, a molded article with an excellent balance between heat resistance and rigidity can be obtained.

[0057] The total content of polymer (A), copolymer (B), and copolymer (C) in the polymer composition (i.e., the content of the 4-methyl-1-pentene polymer) is usually 97.0% by mass or more, preferably 98.0% by mass or more, and more preferably 99.0% by mass or more, when the mass of the polymer composition is 100% by mass. The upper limit of the total content of polymer (A), copolymer (B), and copolymer (C) may be 100% by mass of the polymer composition. When the polymer composition contains other components (for example, other polymer components and additives described below), the upper limit is determined by the content of the other components.

[0058] [Other polymer components] The polymer composition may further contain other polymer components in addition to the polymer (A), copolymer (B), and copolymer (C). Examples of other polymer components include 4-methyl-1-pentene copolymers other than the polymer (A), copolymer (B), and copolymer (C).

[0059] When the polymer composition contains polymer components other than the polymer (A), the copolymer (B), and the copolymer (C), the content of the polymer components is usually 3.0 parts by mass or less, preferably 2.0 parts by mass or less, and more preferably 1.0 part by mass or less, when the total content of the polymer (A), the copolymer (B), and the copolymer (C) is taken as 100 parts by mass.

[0060] [Other additives] The polymer composition may contain other additives known in the art. Examples of other additives include secondary antioxidants, heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers, hydrochloric acid absorbents, and surfactants. These other additives may be used alone or in combination of two or more. The content of the additive is not particularly limited, but is usually 3.0 parts by mass or less, preferably 2.0 parts by mass or less, and more preferably 1.0 part by mass or less, per 100 parts by mass of the 4-methyl-1-pentene polymer.

[0061] <<Physical properties of polymer compositions>> In the 4-methyl-1-pentene polymer contained in the polymer composition, when the total of the structural units (i) derived from 4-methyl-1-pentene and the structural units (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is taken as 100 mol %, the content of the structural units (ii) is preferably 1.0 to 10.0 mol %, more preferably 2.0 to 8.5 mol %, and even more preferably 3.0 to 7.0 mol %. If the 4-methyl-1-pentene type falls within this range, an excellent balance between stretchability and transparency will be achieved. When the polymer composition contains a plurality of 4-methyl-1-pentene polymers, when the sum of the total content of structural units (i) derived from the 4-methyl-1-pentene polymers contained in the polymer composition and the total content of structural units (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) contained in the polymer composition is taken as 100 mol %, it is preferable that the content of structural units (ii) derived from the ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) be within the above range.

[0062] The intrinsic viscosity [η] of the polymer composition, measured in decalin at 135°C by the method described in the examples below, is preferably 1.0 to 4.0 dl / g, more preferably 1.5 to 3.5 dl / g, and even more preferably 2.0 to 3.0 dl / g. A polymer composition having an intrinsic viscosity [η] within the above range has good moldability, and produces particularly good molded articles when injection molded.

[0063] The melt flow rate (MFR) of the polymer composition measured by the method described in the examples below (MFR measured in accordance with JIS K7210 Method B at 260°C and a load of 5 kg) is preferably 1 to 30 g / 10 min, more preferably 3 to 20 g / 10 min, and even more preferably 5 to 15 g / 10 min. A polymer composition having an MFR (260°C, 5 kg load) value within the above range has good moldability, and produces particularly good molded articles when injection molded.

[0064] The melting point (Tm) of the polymer composition measured by the method described in the examples below is preferably from 150 to 300°C, more preferably from 200 to 250°C. A polymer composition having a melting point Tm within the above range has a good balance between heat resistance and moldability.

[0065] The melting enthalpy (ΔH) of the polymer composition measured by the method described in the examples below is preferably 10 to 35 J / g, more preferably 15 to 30 J / g. A polymer composition having a melting enthalpy ΔH value within the above range has a good balance between heat resistance and moldability.

[0066] The crystallization temperature (Tc) of the polymer composition measured by the method described in the examples below is preferably 150 to 250°C, more preferably 180 to 230°C. A polymer composition having a crystallization temperature (Tc) value within the above range has a good balance between heat resistance and moldability.

[0067] The crystallization half time (Tc 1 / 2 ) is 10 to 200 seconds, more preferably 30 to 150 seconds. Half crystallization time (Tc 1 / 2 A polymer composition having a value of ) within the above range has a good balance between heat resistance and moldability.

[0068] <Method for producing polymer composition> The polymer composition can be produced, for example, by mixing the 4-methyl-1-pentene polymer containing the above-mentioned polymer (A), copolymer (B), and copolymer (C), etc., with other polymer components and other additives as necessary. The mixture of polymer (A) and copolymer (B) can also be obtained by the above-mentioned multistage polymerization method.

[0069] The method for mixing the components is not particularly limited, and various known methods can be used. For example, a method can be used in which the components are mixed using an apparatus such as a plastomill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler, a blender, or a kneader-ruder; or a method can be used in which, after the above-mentioned mixing, the resulting mixture is further melt-kneaded using an apparatus such as a single-screw extruder, a twin-screw extruder, a kneader, or a Banbury mixer, and the resulting melt-kneaded product is then granulated or pulverized.

[0070] <Molded body> The molded article of the present invention contains the polymer composition described above. The molded article of the present invention can be obtained by subjecting the polymer composition to known thermoforming processes such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, stretch blow molding, press molding, stamping molding, vacuum forming, calendar molding, filament molding, foam molding, and powder slush molding.

[0071] The polymer composition has excellent moldability, and therefore, a molded article can be suitably produced by the above-mentioned molding method. In particular, the polymer composition has high moldability and can be used by blow molding such as injection blow molding and stretch blow molding, or injection molding, to obtain a suitable molded article. From this perspective, the molded article of the present invention is particularly advantageous when it is a molded article obtained by blow molding, particularly a molded article obtained by injection blow molding, or a molded article obtained by injection molding.

[0072] Suitable embodiments of the molded article of the present invention include hollow molded articles obtained by blow molding such as injection blow molding and stretch blow molding, and hollow molded articles obtained by injection molding.

[0073] A blow-molded article containing the polymer composition can be produced by a commonly known blow-molding method, and an injection-molded article containing the polymer composition can be produced by a commonly known injection-molding method.

[0074] In the present invention, the blow-molded article made of the polymer composition may be formed by injection molding a multilayer preform by co-injecting two or more resin compositions containing the polymer composition, followed by blow molding, to obtain a blow-molded article containing the polymer composition in at least one layer. For the above-described molding, a commonly known apparatus can be used.

[0075] <Uses of molded products> The molded article of the present invention, like molded articles obtained from conventional compositions containing a 4-methyl-1-pentene polymer, has excellent heat resistance, chemical resistance, gas permeability, food hygiene, etc., and further has excellent transparency even after high-pressure steam sterilization (AC sterilization). Therefore, the molded article of the present invention is suitable for use in applications requiring one or more of heat resistance, chemical resistance, gas permeability, food hygiene, and transparency.

[0076] Examples of the molded article of the present invention include films, containers, and packaging materials. In particular, the molded article of the present invention has excellent transparency even after high-pressure steam sterilization (AC sterilization), and therefore can be suitably used in applications where high-pressure steam sterilization (AC sterilization) can be performed. Examples of molded articles used in such applications include laboratory containers such as laboratory equipment, cell culture containers, beverage containers for infants such as baby bottles and mugs, food refill containers, air freshener containers, bottle containers such as cosmetic containers, and gas-permeable containers for ornamental plants. Among these, the molded article is particularly suitable for use in baby bottles, from the viewpoint of excellent transparency even after high-pressure steam sterilization. [Example]

[0077] The present disclosure will be described in more detail below with reference to examples and comparative examples, but the present disclosure is not limited thereto. Note that the number of parts in the examples and comparative examples is by mass unless otherwise specified.

[0078] <Method for measuring polymer properties> The physical properties of the polymers used in the following examples and comparative examples were measured by the following methods.

[0079] [composition] For each of the polymers used in the examples and comparative examples, the amount of the structural unit (i) and the amount of the structural unit (ii) were determined using the following apparatus and conditions: 13 The values ​​were calculated from C-NMR spectra. 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 ethylene, which is a copolymerizable monomer with 4-methyl-1-pentene, and an α-olefin having 3 to 20 carbon atoms.

[0080] The ECP500 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. was used. The solvent was a mixed solvent of o-dichlorobenzene / heavy benzene (80 / 20% by volume), the sample concentration was 55 mg / 0.6 mL, the measurement temperature was 120 °C, and the observed nuclei were 13The measurement was performed using C (125 MHz), the sequence was single pulse proton decoupling, the pulse width was 4.7 μs (45° pulse), the repetition time was 5.5 s, the number of accumulations was more than 10,000, and 27.50 ppm was used as the reference value for the chemical shift. 13 The amounts of structural units derived from 4-methyl-1-pentene and structural units derived from α-olefins were determined by C-NMR spectroscopy.

[0081] [Intrinsic viscosity [η]] The intrinsic viscosity [η] was measured using decalin as a solvent at 135° C. That is, about 20 mg of each of the polymers used in the examples and comparative examples was weighed out, dissolved in 15 mL of decalin, and measured for the specific viscosity η in an oil bath at 135° C. sp After diluting this decalin solution by adding 5 mL of decalin solvent, the specific viscosity η sp This dilution procedure was repeated two more times, and the η when the concentration (C) was extrapolated to 0 was measured. sp The value of / C was calculated as the intrinsic viscosity (see the formula below). [η]=lim(η sp / C) (C→0)

[0082] Melting point (Tm) For each of the polymers used in the examples and comparative examples, the exothermic and endothermic curves were determined using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., and the temperature at the position of the maximum melting peak during temperature rise was taken as the melting point (Tm). The measurement was carried out as follows. Approximately 5 mg of sample was placed in a measurement aluminum pan and heated from 30°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 30°C at a cooling rate of 10°C / min, held at 30°C for 5 minutes, and then heated again from 30°C to 280°C at a heating rate of 10°C / min. The melting peak that appeared during the second heating was taken as the melting point (Tm). When multiple melting peaks were observed, the higher peak temperature was taken as the melting point (Tm).

[0083] [Manufacturing Example 1] In accordance with the polymerization method described in Comparative Example 1 in paragraph

[0158] of WO 2017 / 150265, the proportions of 4-methyl-1-pentene, 1-decene, and hydrogen used were changed so that the physical properties of the resulting 4-methyl-1-pentene copolymer would be the values ​​listed in Table 1, thereby obtaining polymer (A), which is a copolymer of 4-methyl-1-pentene and 1-decene.

[0084] [Manufacturing Example 2] Copolymer (B), which is a copolymer of 4-methyl-1-pentene and 1-decene, was obtained in the same manner as in Production Example 1, except that the proportions of 4-methyl-1-pentene, 1-decene, and hydrogen used were changed so that the physical properties of the resulting 4-methyl-1-pentene copolymer would be the values ​​listed in Table 1.

[0085] [Manufacturing Example 3] In accordance with the polymerization method described in Comparative Example 3 in paragraph

[0159] of WO 2017 / 150265, the proportions of 4-methyl-1-pentene, 1-hexadecene, 1-octadecene, and hydrogen used were changed so that the physical properties of the resulting 4-methyl-1-pentene polymer would be the values ​​shown in Table 1, thereby obtaining copolymer (C), which is a copolymer of 4-methyl-1-pentene with 1-hexadecene and 1-octadecene.

[0086] [Table 1]

[0087] In Table 1, structural unit (i) represents a structural unit derived from 4-methyl-1-pentene, and structural unit (ii) represents a structural unit derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).

[0088] Example 1 [Preparation of polymer composition] The polymer (A) obtained in Production Example 1, the copolymer (B) obtained in Production Example 2, and the copolymer (C) obtained in Production Example 3 were charged into a twin-screw extruder (PCM43, manufactured by Ikegai Corporation, screw diameter: 43 mm) in the blending ratios shown in Table 2, and melt-kneaded in the twin-screw extruder at 280°C and a rotation speed of 150 rpm to obtain a polymer composition (X1).

[0089] [Composition and intrinsic viscosity [η]] The polymer composition (X1) was analyzed using the same method as used to determine the composition of each copolymer blended into the polymer composition (X1), and the contents of the structural units (i) and (ii) in all components of the 4-methyl-1-pentene polymer in the polymer composition (X1) were determined, where the sum of the contents of the structural units (i) and (ii) was defined as 100 mol %. The intrinsic viscosity [η] of the polymer composition (X1) was determined in the same manner as for the intrinsic viscosity [η] of each copolymer blended in the polymer composition (X1). The results are shown in Table 2.

[0090] Melt Flow Rate (MFR) The melt flow rate (MFR) of the polymer composition (X1) was measured under conditions of 260°C, preheating for 340 seconds, and a load of 5 kg in accordance with JIS K7210 method B. The results are shown in Table 2.

[0091] [Temperature rising elution fractionation (TREF)] (a) Operation method A sample solution prepared by completely dissolving the polymer composition (X1) in orthodichlorobenzene at a temperature of 150°C was introduced into a TREF column adjusted to a temperature of 95°C, and then the temperature was gradually lowered to -17°C at a rate of 0.5°C / min to adsorb the sample onto the packing material. After that, the column was kept at 0°C for 30 minutes, and then orthodichlorobenzene was passed through the column and the temperature was kept at 0°C for 10 minutes to elute the components that were not adsorbed by the packing material. This component was designated as the 0°C eluate. Thereafter, the column was heated to 140°C at a heating rate of 1°C / min while orthodichlorobenzene was passed through it, and the polymer components were sequentially eluted. The amount of eluted polymer was measured using the following apparatus under the following measurement conditions, thereby obtaining an elution curve with the elution amount (mass%) on the vertical axis and T (°C) on the horizontal axis. From this dissolution curve, the differential value of the dissolution amount with respect to temperature in the relevant temperature range was calculated, and a dissolution curve with dw / dt on the vertical axis and T (°C) on the horizontal axis was obtained. From these elution curves, the cumulative elution amounts up to 0°C, 20°C and 100°C, as well as the maximum and minimum values ​​of the mass fraction per unit temperature (dW / dT) in the elution temperature range of 40 to 80°C, were determined. The results obtained are shown in Table 2. The measurement equipment and measurement conditions used are shown below.

[0092] (b) Measuring device Equipment: High-throughput composition distribution analyzer CEF (Polymer Char) Detector (built-in): IR5 MCT infrared detector (Polymer Char) Column: CEF column (Polymer Char), length 150 mm, volume 2.6 mL (c) Measurement conditions Mobile phase: o-dichlorobenzene (ODCB), BHT added Sample concentration: 16mg / 8mL Sample filtration: 10μm inline filter ·Injection volume: 0.2mL Detection wavelength: Methylene sensor CH2νa 3.42μm (2,920cm -1 concentration Methyl sensor CH3νa 3.38μm (2,960cm -1 composition

[0093] [Preparation of injection test specimens] The polymer composition (X1) was injected into a square plate shape having a thickness of 0.5 mm or 2 mm using a 70-ton injection molding machine (M70B) manufactured by Meiki Seisakusho Co., Ltd. under conditions of a cylinder temperature of 280°C and a mold temperature of 60°C, to prepare two types of injection test pieces having different thicknesses.

[0094] [Melting point] The exothermic and endothermic curves were determined using a DSC measuring device (model number: DSC220C) manufactured by Seiko Instruments Inc., and the temperature at the melting peak position during temperature rise was taken as the melting point (Tm). The measurement was carried out as follows. Approximately 5 mg of sample was cut from the 0.5 mm thick injection test piece prepared above, placed in an aluminum pan for measurement, and heated from 30 to 280°C at a heating rate of 10°C / min. After holding at 280°C for 5 minutes, the temperature was lowered to 30°C at a cooling rate of 10°C / min, held at 30°C for 5 minutes, and then heated again from 30 to 280°C at a heating rate of 10°C / min. The melting peak that appeared during the second heating was taken as the melting point (Tm). The results are shown in Table 2.

[0095] [Enthalpy of fusion (ΔH)] The exothermic and endothermic curves were determined using a DSC measuring device (model: DSC220C) manufactured by Seiko Instruments Inc., and the melting peak area during the temperature rise was taken as the melting enthalpy (ΔH). The measurement was carried out as follows. Approximately 5 mg of sample was cut from the 0.5 mm thick injection test piece prepared above, placed in an aluminum pan for measurement, and heated from 30 to 280°C at a heating rate of 10°C / min. After holding at 280°C for 5 minutes, the temperature was lowered to 30°C at a cooling rate of 10°C / min, held at 30°C for 5 minutes, and then heated again from 30 to 280°C at a heating rate of 10°C / min. The area of ​​the melting peak that appeared during the second heating was taken as the melting enthalpy (ΔH). The results are shown in Table 2.

[0096] [Crystallization temperature (Tc)] The exothermic and endothermic curves were measured using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., and the temperature at the crystallization peak position during cooling was taken as the crystallization temperature (Tc). The measurement was carried out as follows. Approximately 5 mg of sample was cut from the 0.5 mm thick injection test piece prepared above, placed in an aluminum pan for measurement, and heated from 30 to 280°C at a heating rate of 10°C / min. After holding at 280°C for 5 minutes, the temperature was lowered to 30°C at a cooling rate of 10°C / min, held at 30°C for 5 minutes, and then heated again from 30 to 280°C at a heating rate of 10°C / min. The crystallization peak that appeared during the first cooling was taken as the crystallization temperature (Tc). The results are shown in Table 2.

[0097] [Half crystallization time (Tc 1 / 2 )] The exothermic and endothermic curves were measured using a DSC measuring device (DSC8500) manufactured by PerkinElmer Co., Ltd., and the half-crystallization time (Tc 1 / 2 ) was measured. The measurement was carried out as follows. Approximately 5 mg of sample was cut out from the 0.5 mm thick injection test piece prepared above, placed in an aluminum pan for measurement, and heated from 30°C to 280°C at a heating rate of 500°C / min. After holding at 280°C for 10 minutes, the temperature was lowered to 215°C at a cooling rate of 500°C / min, and the crystallization peak at 215°C was measured. The half-crystallization time (Tc 1 / 2 If no peak appears in the above test, the half-crystallization time (Tc 1 / 2 The results are shown in Table 2.

[0098] [Measurement of total haze and total light transmittance] The 2 mm thick injection test piece prepared above was used to measure the haze and transmittance in accordance with JIS K 7136 using a Nippon Denshoku Industries Co., Ltd. haze and transmittance meter (model: NDH-2000 (D 65 The total haze and total light transmittance were calculated by measuring the proportion of transmitted light that deviated by 2.5° or more from the incident light due to forward scattering, using a light source). The results are shown in Table 2.

[0099] [Measurement of total haze and total light transmittance after autoclaving] The 2mm thick injection test specimens prepared above were subjected to high-pressure steam sterilization at 100°C for 60 minutes using a Tomy Industries Co., Ltd. high-pressure steam sterilizer (model number: LSX-300). The total haze and total light transmittance of the injection test specimens were measured within one hour of high-pressure steam sterilization using the method described above, and these were used as indicators of transparency. The results are shown in Table 2. It can be said that the lower the total haze value of the injection test piece after high-pressure steam sterilization, the better the transparency even when high-pressure steam sterilization is performed.

[0100] [Moldability] The polymer composition (X1) was used to form a blow-molded article. <Molding 1: Stretch blow molding using mold I> (Preparation of preform A) Using an injection molding machine (model number: FNX-140) manufactured by Nissei Plastic Industrial Co., Ltd., polymer composition (X1) was processed under conditions of a cylinder temperature of 260 to 280°C and a mold temperature of 22°C to produce preform A having an outer diameter of 56 mm, a height of 45 mm, and a mass of 36 g.

[0101] (Stretch blow molding of preform A) The preform A was blow molded using an injection blow molding machine manufactured by Frontier Corporation, with the surface temperature adjusted to 200°C to 210°C, using a mold I capable of producing a 231 cc container (longitudinal stretch ratio: 1.2 times, transverse stretch ratio: 1.3 times, total stretch ratio: 1.6 times), and moldability was evaluated. Air blowing was performed in two stages, with a primary pressure of 1.2 MPa and a secondary pressure of 1.8 MPa.

[0102] (evaluation) The moldability was evaluated according to the following criteria, and the evaluation results are shown in Table 2. [Evaluation criteria] Good: The standard deviation of the thickness measured at 5 mm intervals from the part 10 mm from the bottom to the part 45 mm from the bottom of the molded article is less than 0.28 mm. ×: The standard deviation of the thickness measured at 5 mm intervals from the part 10 mm from the bottom to the part 45 mm from the bottom of the molded article is 0.28 mm or more.

[0103] <Examples 2 and 3 and Comparative Examples 1 and 2> Polymer compositions (X2) to (X5) were prepared in the same manner as in Example 1, except that the blending amounts of polymer (A), copolymer (B), and copolymer (C) were changed as shown in Table 2. The physical properties of the resulting polymer compositions and the physical properties of injection-molded articles of the resulting polymer compositions were measured. Transparency was evaluated by measuring the total haze and total light transmittance before and after high-pressure steam sterilization in the same manner as in Example 1. Furthermore, blow molding was performed in the same manner as in Example 1, and moldability was evaluated. The results are shown in Table 2.

[0104] [Table 2]

[0105] In Table 2, "(II) - (I)" means the value obtained by subtracting the cumulative elution amount up to 20°C (I) from the cumulative elution amount up to 100°C (II) in temperature-rising elution fractionation. The polymer compositions (X1) to (X3) of Examples 1 to 3 were molded into bottle shapes using mold I, and all were able to be stretch-blow molded without any wall thickness deviation. Furthermore, all of the polymer compositions (X1) to (X3) of Examples 1 to 3 before autoclaving had low total haze and high total light transmittance, yielding molded articles with high transparency. Furthermore, all of the polymer compositions (X1) to (X3) of Examples 1 to 3 had low total haze and high total light transmittance even after autoclaving, demonstrating that molded articles with high transparency could be obtained even after autoclaving. On the other hand, in (X5) Comparative Example 2, which used a composition that did not satisfy requirement (1), molding defects were confirmed when blow molding was performed. In (X4) Comparative Example 1, which used a composition that did not satisfy requirement (2), moldability was good, but the total haze increased after high-pressure steam sterilization, and the transparency of the molded product was impaired.

Claims

1. Contains a 4-methyl-1-pentene polymer, A polymer composition satisfying the following requirements (1) and (2): (1) The cumulative elution amount up to 20°C in temperature rising elution fractionation is 4.0% by mass or more; (2) In temperature rising elution fractionation, the value obtained by subtracting the cumulative elution amount up to 20°C from the cumulative elution amount up to 100°C is 4.0 mass% or more.

2. the maximum value of the mass fraction per unit temperature (dW / dT) in the elution temperature range of 40°C to 80°C in temperature rising elution fractionation is 2.00% by mass / °C or less; 2. The polymer composition according to claim 1, wherein the minimum value of the mass fraction per unit temperature (dW / dT) in the elution temperature range of 40°C to 80°C in temperature rising elution fractionation is 0.10% by mass / °C or more.

3. 3. The polymer composition according to claim 1, wherein the cumulative elution amount up to 100°C in temperature rising elution fractionation is 42.0 to 62.0% by mass.

4. The 4-methyl-1-pentene polymer is 0.5 to 30% by mass of a 4-methyl-1-pentene polymer (A) satisfying the following requirement (A-i); 0.5 to 30% by mass of a 4-methyl-1-pentene copolymer (B) satisfying the following requirement (Bi); 40 to 99 mass% of a 4-methyl-1-pentene copolymer (C) satisfying the following requirement (C-i) (wherein the total content of the polymer (A), the copolymer (B), and the copolymer (C) is 100 mass%); (A-i) When the total of the structural units (i) derived from 4-methyl-1-pentene and the structural units (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is taken as 100 mol%, the content of the structural units (i) is more than 98.0 mol% but not more than 100 mol%, and the content of the structural units (ii) is at least 0 mol% but less than 2.0 mol%; (Bi) When the total of the structural units (i) derived from 4-methyl-1-pentene and the structural units (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is taken as 100 mol %, the content of structural units (i) is 90.0 mol % or less, and the content of structural units (ii) is 10.0 mol % or more; (C-i) When the total of the structural units (i) derived from 4-methyl-1-pentene and the structural units (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is taken as 100 mol %, the content of structural units (i) is more than 90.0 mol % and 98.0 mol % or less, and the content of structural units (ii) is 2.0 mol % or more and less than 10.0 mol %.

5. The polymer composition according to claim 4, wherein the polymer (A), the copolymer (B), and the copolymer (C) each have an intrinsic viscosity in decalin at 135°C of 1.0 to 5.0 dL / g.

6. The polymer (A) has a melting point of 200 to 250°C, The melting point of the copolymer (B) is 200°C or less, or no melting point is observed, The polymer composition according to claim 4, wherein the melting point of the copolymer (C) is 200 to 250°C.

7. A molded article comprising the polymer composition according to claim 1 or 2.

8. The molded article according to claim 7, which is a bottle container.

9. The molded article according to claim 7, which is a baby bottle.

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