Resin composition, molding, and film

Abstract

To provide a resin composition which gives a molding having excellent impact resistance at a low temperature and can be injection-molded.SOLUTION: The resin composition contains: a 4-methyl-1-pentene-based polymer (A) which contains a constituent unit derived from 4-methyl-1-pentene and a constituent unit derived from a C10-20 α-olefin; and a styrenic elastomer (B) which is a hydrogenated product of a block copolymer of a polystyrene block and a diene block, the content of the polystyrene block being more than 10 mass% and 50 mass% or less based on the total mass of the styrenic elastomer (B). The content of the 4-methyl-1-pentene-based polymer (A) is more than 50 mass% and less than 100 mass% based on the total mass of the resin composition, and the content of the styrenic elastomer (B) is 50 mass% or less based on the total mass of the resin composition. A molding and a film comprising the resin composition are also provided.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] 4-Methyl-1-pentene polymers, which have 4-methyl-1-pentene as the main monomer, are widely used in various applications due to their excellent releasability, heat resistance, water resistance, and solvent resistance. For example, films are used as release films for flexible printed circuit boards (FPCs) and release films for composite material molding, taking advantage of their features such as high melting point and good releasability, and molded products are used for laboratory equipment and mandrels for rubber hose manufacturing, taking advantage of their features such as chemical resistance and water resistance. On the other hand, 4-methyl-1-pentene polymers are not only used alone, but are also used in compositions with elastomers.

[0003] For example, Patent Document 1 discloses a resin composition that is easily moldable and processable, and is made of a thermoplastic resin and an inorganic filler, and that contains a 4-methyl-1-pentene / α-olefin copolymer (A), an inorganic filler (B), and a specific thermoplastic elastomer (C) in a specific blending ratio.

[0004] For example, Patent Document 2 discloses a sheet or film with suppressed blocking, which is made of a composition containing a polymer (A) containing one or more polymers selected from the group consisting of a 4-methyl-1-pentene polymer (A1) and a styrene elastomer (A2), and a silylated polyolefin (B).

[0005] Furthermore, for example, Patent Document 3 discloses a composition that has good fit and good feel at low temperatures, the composition comprising a 4-methyl-1-pentene polymer (a) and a styrene-based elastomer (b), the 4-methyl-1-pentene polymer (a) comprising structural units derived from 4-methyl-1-pentene and structural units derived from an α-olefin having 2 to 10 carbon atoms other than 4-methyl-1-pentene, the styrene-based elastomer (b) being a hydrogenated block copolymer of a polystyrene block and a diene block, the content of the polystyrene block relative to the total amount of the styrene-based elastomer (b) being more than 0.0% by mass and not more than 50% by mass, and the content of the styrene-based elastomer (b) being 5 parts by mass or more and not more than 500 parts by mass relative to 100 parts by mass of the 4-methyl-1-pentene polymer (a).

[0006] Furthermore, for example, Patent Document 4 discloses a 4-methyl-1-pentene resin composition that maintains heat resistance and shape retention at high temperatures while also exhibiting significantly improved fracture resistance at low temperatures. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2022 / 158511 [Patent Document 2] International Publication No. 2022 / 202622 [Patent Document 3] International Publication No. 2022 / 270581 [Patent Document 4] JP 2013-216817 A Summary of the Invention [Problem to be solved by the invention]

[0008] However, none of the above-mentioned Patent Documents 1 to 4 adequately examines the impact resistance at low temperatures of molded articles obtained from injection-moldable resin compositions, and further improvements are desired.

[0009] The problem to be solved by one embodiment of the present invention is to provide a resin composition which is injection moldable and which provides a molded article having excellent impact resistance at low temperatures. The problem to be solved by another embodiment of the present invention is to provide a molded article and a film having excellent impact resistance at low temperatures. [Means for solving the problem]

[0010] Means for solving the above problems include the following aspects. <1> A 4-methyl-1-pentene polymer (A) containing a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin having 10 to 20 carbon atoms; a styrene-based elastomer (B) which is a hydrogenated block copolymer of a polystyrene block and a diene block, and the content of the polystyrene block relative to the total mass of the styrene-based elastomer (B) is more than 10 mass% and not more than 50 mass%; Including, A resin composition, wherein the content of the 4-methyl-1-pentene polymer (A) is more than 50 mass% and less than 100 mass% based on the total mass of the resin composition, and the content of the styrene elastomer (B) is 50 mass% or less based on the total mass of the resin composition. <2> The content of the structural units derived from an α-olefin having 10 to 20 carbon atoms in the 4-methyl-1-pentene polymer (A) is 1 to 20 mol % (provided that the total molar number of the structural units derived from 4-methyl-1-pentene and the structural units derived from an α-olefin having 10 to 20 carbon atoms is 100 mol %); <1> The resin composition according to claim 1. <3> The α-olefin having 10 to 20 carbon atoms is at least one selected from the group consisting of 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene. <1> or <2> The resin composition according to claim 1. <4> <1> ~ <3> A molded article comprising the resin composition according to any one of the above items. <5> <1> ~ <3> A film comprising the resin composition according to any one of the above items. Effect of the Invention

[0011] According to one embodiment of the present invention, there is provided a resin composition which is injection moldable and which provides a molded article having excellent impact resistance at low temperatures. Also, according to one embodiment of the present invention, there is provided a molded article and a film having excellent impact resistance at low temperatures. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] 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, the terms "polymer" and "(co)polymer" are used to include homopolymers and copolymers, unless otherwise specified. In this specification, the use of "to" indicating a numerical range means that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, the units written either before or after "~" indicating a numerical range refer to the same units unless otherwise specified. As used herein, a combination of two or more preferred embodiments is a more preferred embodiment. In addition, unless otherwise specified in this specification, each component in the composition or each structural unit in the polymer may be contained alone or in combination of two or more types. In this specification, the amount of each component in a composition or each structural unit in a polymer means, when a plurality of substances or structural units corresponding to each component or each structural unit in a polymer are present in the composition, the total amount of the corresponding substance present in the composition or each of the plurality of structural units present in the polymer, unless otherwise specified. Moreover, the various monomers in this specification may be derived from fossil raw materials or from biomass. The present invention will be described in detail below.

[0013] <Resin composition> The resin composition according to the present invention includes a 4-methyl-1-pentene polymer (A) containing a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin having 10 to 20 carbon atoms, and a styrene-based elastomer (B) which is a hydrogenated block copolymer of a polystyrene block and a diene block, and in which the content of the polystyrene block relative to the total mass of the styrene-based elastomer (B) is more than 10 mass% and less than 50 mass%, wherein the content of the 4-methyl-1-pentene polymer (A) is more than 50 mass% and less than 100 mass%, relative to the total mass of the resin composition, and the content of the styrene-based elastomer (B) is 50 mass% or less, relative to the total mass of the resin composition. The resin composition according to the present invention has the above-mentioned constitution, and thus can be injection molded, and the molded article obtained has excellent impact resistance at low temperatures (hereinafter, may be referred to as "low-temperature impact resistance"). The reason for this is not clear, but the following estimated mechanism is presumed. The resin composition contains a specific amount of a specific 4-methyl-1-pentene polymer (A) and a specific styrene elastomer (B). The styrene elastomer (B) is a hydrogenated block copolymer of a polystyrene block and a diene block, and the content of the polystyrene block relative to the total mass of the styrene elastomer (B) exceeds 10% by mass. It is presumed that the polystyrene block is likely to form physical crosslinks, particularly at low temperatures, and thus rubber elasticity is exhibited. Therefore, the impact resistance at low temperatures is excellent. In addition, the content of the polystyrene block relative to the total mass of the styrene elastomer (B) is 50% by mass or less, so that the glass transition temperature in the composition is likely to be low, and the impact resistance at low temperatures is excellent. In addition, it is presumed that the content of the 4-methyl-1-pentene polymer (A) in the composition is more than 50% by mass but less than 100% by mass, and the content of the styrene elastomer (B) is 50% by mass or less relative to the total mass of the resin composition, so that the rigidity derived from the 4-methyl-1-pentene polymer (A) and the impact absorption properties derived from the styrene elastomer (B) are in harmony, resulting in better impact resistance at low temperatures. In addition, it is presumed that the content of the polystyrene block in the styrene elastomer (B) exceeds 10% by mass, which improves compatibility with the thermoplastic resin 4-methyl-1-pentene polymer (A), making molding easier, and thus making injection molding possible. In addition, it is presumed that the diene block portion in the styrene elastomer is flexible, so that appropriate rubber elasticity can be obtained at low temperatures while maintaining flexibility. Each component contained in the resin composition according to the present invention will be described in detail below.

[0014] <<4-methyl-1-pentene polymer (A)>> The 4-methyl-1-pentene polymer (A) contains a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin having 10 to 20 carbon atoms. The 4-methyl-1-pentene polymer is a polymer containing 4-methyl-1-pentene as a main component. The main component mentioned here means the component that is the most abundant among the components that constitute the polymer, and the content of the structural unit derived from 4-methyl-1-pentene described below is preferably more than 50 mol%, more preferably 52 mol% or more, and even more preferably 55 mol% or more (however, the total number of moles of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from an α-olefin having 10 to 20 carbon atoms is 100 mol%). There is no particular upper limit to the content of the structural unit derived from 4-methyl-1-pentene, but it is preferably 99.5 mol% or less, more preferably 99 mol% or less. In this specification, the content (mol%) of each structural unit in the above polymer is 13 This is measured by a C-NMR measurement method, and specifically, it is determined by the method described in the examples below.

[0015] From the standpoint of excellent heat resistance, the content of structural units derived from 4-methyl-1-pentene is preferably 80 to 99.9 mol %, and more preferably 96 to 98 mol %. However, the total number of moles of the structural units derived from 4-methyl-1-pentene and the structural units derived from an α-olefin having 10 to 20 carbon atoms is 100 mol %.

[0016] The α-olefin having 10 to 20 carbon atoms is not particularly limited and may be a linear, branched, or cyclic α-olefin. Among these, the α-olefin having 10 to 20 carbon atoms is preferably a linear α-olefin from the viewpoint of obtaining a polymer having high strength.

[0017] The α-olefin having 10 to 20 carbon atoms is preferably an α-olefin having 12 to 20 carbon atoms, and more preferably an α-olefin having 12 to 18 carbon atoms.

[0018] Examples of the α-olefin having 10 to 20 carbon atoms include 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene, 1-nonadecene, 1-icosene, etc. Among these, the α-olefin having 10 to 20 carbon atoms is preferably at least one selected from the group consisting of 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene, and more preferably 1-hexadecene and 1-octadecene.

[0019] The content of the structural units derived from an α-olefin having 10 to 20 carbon atoms in the 4-methyl-1-pentene polymer (A) is preferably 0.1 to 20 mol %, and more preferably 2 to 8 mol % (however, the total molar number of the structural units derived from 4-methyl-1-pentene and the structural units derived from an α-olefin having 10 to 20 carbon atoms is 100 mol %). The structural unit derived from an α-olefin having 10 to 20 carbon atoms may be one type alone, or two or more types may be included.

[0020] <<Other building blocks>> The 4-methyl-1-pentene polymer (A) may contain structural units other than the structural units derived from 4-methyl-1-pentene and the structural units derived from an α-olefin having 10 to 20 carbon atoms (hereinafter also referred to as "other structural units"), provided that the effects of the present invention are not impaired.

[0021] Specific examples of the monomers that form the other structural units include cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, halogenated olefins, and the like.

[0022] Examples of the cyclic olefin, aromatic vinyl compound, conjugated diene, non-conjugated polyene, functional vinyl compound, hydroxyl group-containing olefin, and halogenated olefin include the compounds described in paragraphs 0034 to 0041 of JP2013-169685A.

[0023] Among these, as the monomers forming the other structural units, cyclic olefins and aromatic vinyl compounds are preferred, with vinylcyclohexane and styrene being particularly preferred.

[0024] The content of the other structural units is preferably from 0 to 10 mol %, more preferably from 0 to 5 mol %, and even more preferably from 0 to 3 mol %, based on all structural units of the 4-methyl-1-pentene polymer (A). The other structural units may be contained in one type only, or in two or more types.

[0025] The melt flow rate (MFR) of the 4-methyl-1-pentene polymer (A) measured in accordance with ASTM D1238 at 260°C under a load of 5 kg is preferably 0.1 to 100 g / 10 min, more preferably 10 to 70 g / 10 min, and further preferably 15 to 30 g / 10 min.

[0026] The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A) in decalin at 135° C. is preferably 0.01 to 5.0 dL / g, more preferably 0.1 to 4.0 dL / g, even more preferably 0.5 to 3.0 dL / g, and particularly preferably 1.0 to 2.8 dL / g, from the viewpoint of improving the flexibility and mechanical strength of the composition. The value of the intrinsic viscosity [η] can be adjusted, for example, by the amount of hydrogen added during polymerization when the 4-methyl-1-pentene polymer (A) is produced.

[0027] The density of the 4-methyl-1-pentene polymer (A) is preferably 810 to 850 kg / m 3 and more preferably 825 to 845 kg / m 3 The density is determined by the method described in the Examples below.

[0028] The 4-methyl-1-pentene polymer (A) has a melting point (Tm) measured by differential scanning calorimetry (DSC) of preferably 180 to 250°C, more preferably 190 to 250°C, further preferably 195 to 240°C, and particularly preferably 200 to 235°C. The melting point (Tm) is determined by the method described in the Examples below.

[0029] The melting point (Tm) value tends to depend on the stereoregularity of the polymer and the content of structural units derived from an α-olefin having 10 to 20 carbon atoms, and can therefore be appropriately adjusted by using a stereospecific catalyst for olefin polymerization and further controlling the content of structural units derived from an α-olefin having 10 to 20 carbon atoms.

[0030] The content of the 4-methyl-1-pentene copolymer (A) is more than 50 mass% and less than 100 mass%, preferably 55 mass% to 95 mass%, and more preferably 55 mass% to 90 mass%, based on the total mass of the resin composition. The 4-methyl-1-pentene polymer (A) may be one type alone or may contain two or more types.

[0031] [Method for producing 4-methyl-1-pentene polymer] The 4-methyl-1-pentene polymer (A) can be obtained by polymerizing 4-methyl-1-pentene, an α-olefin having 10 to 20 carbon atoms, and the monomers forming the other structural units.

[0032] The polymerization method is not particularly limited, and can be produced by, for example, a gas phase method, a solution method, a slurry method, etc. As the catalyst, in addition to conventionally known olefin polymerization catalysts such as vanadium catalysts, titanium catalysts, and magnesium-supported titanium catalysts, for example, metallocene catalysts can be produced using catalysts described in WO 2001 / 53369, WO 2001 / 27124, WO 2006 / 054613, WO 2014 / 050817, JP-A-3-193796, or JP-A-2-41303.

[0033] The 4-methyl-1-pentene polymer (A) may be obtained by single-stage polymerization of 4-methyl-1-pentene, an α-olefin having 10 to 20 carbon atoms, and, if necessary, a monomer forming the other structural unit in a single polymerization step, or by mixing 4-methyl-1-pentene (co)polymers produced in separate steps. Furthermore, the 4-methyl-1-pentene (co)polymer may be continuously polymerized in multiple steps through multiple polymerization steps. The 4-methyl-1-pentene polymer (A) may also be obtained by heat treating a 4-methyl-1-pentene (co)polymer once produced using the above catalyst or the like in an extruder, mixer or the like.

[0034] <<Styrene-based elastomer (B)>> The resin composition according to the present invention contains a styrene-based elastomer (B) which is a hydrogenated block copolymer of a polystyrene block and a diene block, and in which the content of the polystyrene block relative to the total mass of the styrene-based elastomer (B) is more than 10 mass% and not more than 50 mass%. The styrene-based elastomer (B) is a hydrogenated block copolymer of a polystyrene block and a diene block. The hydrogenated block copolymer can be produced, for example, by a known method from the block copolymer in an inert solvent in the presence of a hydrogenation catalyst.

[0035] The hydrogenation of the block copolymer may be such that a part of the block copolymer is hydrogenated, or the whole of the block copolymer is hydrogenated. From the viewpoint that hydrogenation reduces unsaturated bonds and makes it easier to obtain flexibility, heat resistance, mechanical properties, etc., the hydrogenation rate of the block copolymer is preferably such that 50% or more, more preferably 80% or more of the olefinic double bonds in the copolymer block are hydrogenated.

[0036] The content of the polystyrene block relative to the total mass of the styrene-based elastomer (B) (hereinafter, may be referred to as the "styrene content") is more than 10 mass% and not more than 50 mass%, preferably more than 10 mass% and not more than 30 mass%, more preferably more than 10 mass% and not more than 20 mass%, and even more preferably more than 10 mass% and not more than 15 mass%.

[0037] The styrene-based elastomer (B) is preferably at least one copolymer selected from the group consisting of hydrogenated styrene-butadiene rubber, hydrogenated styrene-butadiene block copolymer (SEBS), hydrogenated styrene-isoprene block copolymer (SEPS) and hydrogenated styrene-isoprene-butadiene block copolymer (SEEPS), and from the viewpoint of excellent heat resistance and low-temperature tensile elongation, is more preferably hydrogenated styrene-butadiene block copolymer (SEBS). The styrene-based elastomer (B) may be a compound having a structure mainly composed of vinyl bonds (1,2-vinyl bonds are 30 to 50%), that is, a compound called vinyl SEBS, vinyl SEPS, or vinyl SEEPS.

[0038] The styrene-based elastomer (B) may be obtained by a normal method such as anionic polymerization or cationic polymerization, or may be a commercially available product. Examples of commercially available products of the styrene-based elastomer (B) include Kraton, a product name of Kraton Polymers, Tuftec and SOE, a product name of Asahi Kasei Corporation, Septon and Hybler, a product name of Kuraray Co., Ltd., and Dynaron, a product name of JSR Corporation.

[0039] The melt flow rate (MFR) of the styrene-based elastomer (B), measured in accordance with ASTM D1238 at 190° C. under a load of 2.16 kg, is preferably 0.1 to 20 g / 10 min, more preferably 0.5 to 15 g / 10 min.

[0040] The content of the styrene-based elastomer (B) is 50 mass% or less, preferably 5 to 50 mass%, more preferably 10 to 50 mass%, even more preferably 20 to 50 mass%, and particularly preferably 30 to 45 mass%, based on the total mass of the composition. The styrene-based elastomer (B) may be one type alone, or two or more types may be included.

[0041] [Other ingredients] The resin composition may further contain components other than the 4-methyl-1-pentene polymer (A) and the styrene elastomer (B) (hereinafter also referred to as "other components"), if necessary. Examples of other components include additives such as foaming agents, heat stabilizers, antioxidants, ultraviolet absorbers, pigments, antistatic agents, copper damage inhibitors, flame retardants, neutralizing agents, plasticizers, nucleating agents, weather stabilizers, light stabilizers, antiaging agents, fatty acid metal salts, softeners, dispersants, colorants, lubricants, natural oils, synthetic oils, and waxes, as well as polymers other than the 4-methyl-1-pentene polymer (A) and the styrene elastomer (B) (hereinafter also referred to as "other polymers"). In order to adjust the temperature at which the loss tangent (tan δ) of the solid viscoelasticity of the composition shows a maximum value and the maximum value of the loss tangent, the type and the amount of a plasticizer, a softener, a natural oil, and a synthetic oil may be controlled.

[0042] [Other polymers] Suitable examples of the other polymers include 4-methyl-1-pentene polymers other than the 4-methyl-1-pentene polymer (A). Examples of 4-methyl-1-pentene polymers other than the 4-methyl-1-pentene polymer (A) include 4-methyl-1-pentene-α-olefin copolymers containing structural units derived from 4-methyl-1-pentene and structural units derived from an α-olefin having 2 to 9 carbon atoms other than 4-methyl-1-pentene. The α-olefin having 2 to 9 carbon atoms is preferably an α-olefin having 2 to 4 carbon atoms, and more preferably an α-olefin having 2 or 3 carbon atoms. Examples of the α-olefin having 2 to 9 carbon atoms include ethylene, propylene, 1-butene, and 1-pentene. From the viewpoint of improving flexibility, the α-olefin having 2 to 9 carbon atoms is preferably propylene. The above α-olefins having 2 to 9 carbon atoms may be used alone or in combination of two or more kinds.

[0043] The content of structural units derived from α-olefins having 2 to 9 carbon atoms other than 4-methyl-1-pentene is preferably 1 to 40 mol%, more preferably 10 to 30 mol%, and even more preferably 15 to 28 mol%, and the content of structural units derived from 4-methyl-1-pentene is preferably 60 to 99 mol%, more preferably 70 to 90 mol%, and even more preferably 72 to 85 mol% (however, the total number of moles of the structural units derived from 4-methyl-1-pentene and the structural units derived from α-olefins having 2 to 9 carbon atoms other than 4-methyl-1-pentene is 100 mol%).

[0044] The content of the other polymer is preferably from 5 to 30% by mass, and more preferably from 10 to 25% by mass, based on the total mass of the resin composition. The other polymers may be used alone or in combination of two or more.

[0045] The method for producing the resin composition is not particularly limited, and various known methods can be used. For example, the resin composition can be prepared by dry blending the above-mentioned 4-methyl-1-pentene polymer (A), the styrene elastomer (B), and other components as necessary, using a Henschel mixer, a tumbler blender, a V-blender, or the like, by dry blending, melt kneading the components using a single-screw extruder, a multi-screw extruder, a Banbury mixer, or the like, or by stirring and mixing the components in the presence of a solvent.

[0046] <Molded body> The molded article according to the present invention comprises the above-mentioned resin composition. The molded article is not particularly limited, and may be a molded article obtained by a known thermoforming method such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, stamping molding, vacuum molding, calendar molding, filament molding, foam molding, powder slush molding, 3D modeling, or microwave heating molding.

[0047] The shape of the molded product is not particularly limited and may be a desired shape depending on the purpose, for example, a plate shape, a film shape, a tube (cylindrical shape), a fiber shape, a bottle shape, etc. The resin composition of the present invention can be injection molded, and therefore is also suitable as a film containing the resin composition. EXAMPLES

[0048] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0049] <Production Example 1> [Production of 4-methyl-1-pentene polymer (A-1)] In Example 17 of WO 2006 / 054613, the amount of monomer charged was changed so that the content (mol%) of the 4-methyl-1-pentene-derived structural unit and the structural unit derived from a mixture of 1-hexadecene and 1-octadecene in the resulting copolymer was the content shown in Table 1 below, and the amount of hydrogen during polymerization was adjusted so that the melt flow rate (MFR) was the melt flow rate shown in Table 1 below, thereby obtaining a 4-methyl-1-pentene-based copolymer (A-1). The physical properties of the 4-methyl-1-pentene-based copolymer (A-1) are shown in Table 1 below.

[0050] <Production Example 2> [Production of 4-methyl-1-pentene polymer (A-2)] Preparation Example 1: Preparation of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride Using the method described in Preliminary Experiment 5 (paragraphs

[0346] to

[0348] ) of WO 2014 / 123212, (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride was synthesized.

[0051] Synthesis Example 1-1: Production of olefin polymerization catalyst In a 200 mL three-neck flask equipped with a stirrer and thoroughly purged with nitrogen, 30 mL of purified decane and granular D 50A solid polymethylaluminoxane having a diameter of 28 μm and an aluminum atom content of 43 mass% (synthesized using the method described in International Publication No. 2014 / 123212) was charged at 14.65 mmol in terms of aluminum atoms to obtain a suspension. 50.0 mg (0.0586 mmol) of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) zirconium dichloride obtained in Preparation Example 1 above was added to the suspension while stirring as a 4.58 mmol / L toluene solution. After 1 hour, stirring was stopped, and the resulting mixture was washed with 100 mL of decane by decantation, and then decane was added to obtain 50 mL of a slurry liquid (zirconium atom loading rate 98%).

[0052] Synthesis Example 1-2: Preparation of prepolymerization catalyst components The slurry liquid prepared in the above Synthesis Example 1-1 was charged into a reactor equipped with a stirrer and fully purged with nitrogen. 1.0 mL of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol / mL in terms of aluminum atom) was added to the above slurry liquid under a nitrogen stream at 25°C. After cooling to 15°C, 10 mL of 4-methyl-1-pentene was charged into the reactor over 60 minutes. The start of the charging of 4-methyl-1-pentene was regarded as the start of prepolymerization. Stirring was stopped 2 hours after the start of prepolymerization, and the resulting mixture was washed three times with 100 mL of decane by decantation. The prepolymerization catalyst component was a decane slurry (9.5 g / L, 0.56 mmol / L in terms of zirconium atom).

[0053] At room temperature and under a nitrogen stream, 425 mL of purified decane was charged into a SUS polymerization vessel equipped with a stirrer having an internal volume of 1 L, and the temperature was raised to 40°C. After reaching 40°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol / mL in terms of aluminum atoms) was charged, and then 0.00175 mmol in terms of zirconium atoms of the decane slurry of the prepolymerization catalyst component of Synthesis Example 1-2 was charged. 23.75 NmL of hydrogen was charged, and then a mixture of 230 mL of 4-methyl-1-pentene and 22.4 mL of Linearene 168 (Idemitsu Kosan Co., Ltd., a mixture of 1-hexadecene and 1-octadecene) was continuously charged into the polymerization vessel at a constant rate over 2 hours. The start of polymerization was the start of the addition of the mixed liquid, and the temperature was maintained at 45°C for 4.5 hours. 23.75 NmL of hydrogen was added 1 hour and 2 hours after the start of polymerization. 4.5 hours after the start of polymerization, the temperature was lowered to room temperature, the pressure was released, and the polymerization liquid containing a white solid was immediately filtered to obtain a solid substance. The solid substance was dried under reduced pressure at 80°C for 8 hours to obtain a 4-methyl-1-pentene polymer (A-2). The yield was 142 g. The content of the structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (A-2) was 96.5 mol%, and the content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms was 3.5 mol%. The melting point (Tm) of the 4-methyl-1-pentene polymer (A-2) was 201°C, and the intrinsic viscosity [η] (in decalin at 135°C) was 1.0 dl / g. Other physical properties of the 4-methyl-1-pentene polymer (A-2) are shown in Table 1.

[0054] <Production Example 3> [Production of other polymers (C-1)] The 4-methyl-1-pentene-α-olefin copolymer (A) used in the examples of WO 2022 / 158511 was synthesized in the same manner as described in paragraphs

[0126] to

[0128] of WO 2022 / 158511 to obtain another polymer (C-1). For the other polymer (C-1) obtained, the composition, melt flow rate (MFR), melting point and density were measured by the following measuring methods. The results are shown in Table 1.

[0055] [Table 1]

[0056] <Melt flow rate (MFR)> The melt flow rate (MFR) was measured at 260°C and a load of 5 kg according to ASTM D1238. The MFR of other polymers was measured at a temperature of 230°C and a load of 2.16 kg.

[0057] <Melting point (Tm)> An exothermic / endothermic curve was obtained using a differential scanning calorimeter (DSC) measuring device (DSC220C) manufactured by Seiko Instruments Inc., and the temperature at the maximum melting peak position during heating was taken as the melting point (Tm). The measurement was performed as follows. First, about 5 mg of pellet sample was packed in a measurement aluminum pan, heated from 20°C to 280°C at a heating rate of 10°C / min, held at 280°C for 5 minutes, cooled to 20°C at a cooling rate of 10°C / min, held at 20°C for 5 minutes, heated again from 20°C to 280°C at a heating rate of 10°C / min, and cooled again to 50°C at a cooling rate of 50°C / min. The melting peak that appeared during the second heating was taken as the melting point (Tm). When there were multiple melting peaks, the value with the strongest peak intensity was taken as the melting point.

[0058] <density> Measurements were performed in accordance with JIS K7112 (density gradient tube method).

[0059] <Polymer composition measurement> The content (mol%) of 4-methyl-1-pentene-derived structural units and α-olefin-derived structural units was measured using the following apparatus and conditions: 13 Calculated from C-NMR spectrum. The apparatus used was a Bruker AVANCEIIIcryo-500 nuclear magnetic resonance apparatus, the solvent was a mixed solvent of o-dichlorobenzene / benzene-d6 (4 / 1 v / v), the sample concentration was 55 mg / 0.6 mL, the measurement temperature was 120°C, and the observed nuclei were: 13 The chemical shift was measured using the 128 ppm peak of benzene-d6 as the reference value under the following conditions: C (125 MHz), sequence: single pulse proton broadband decoupling, pulse width: 5.0 μsec (45° pulse), repetition time: 5.5 sec, and number of accumulations: 64. The content (mol%) of the structural units derived from each monomer was calculated using the integral value of the main chain methine signal.

[0060] [Styrene-based elastomer (B-1)] As the styrene-based elastomer (B-1), a hydrogenated styrene-isoprene-butadiene block copolymer (vinyl SEEPS) (product name: "Hybra 7311F", manufactured by Kuraray Co., Ltd.), polystyrene block content: 12% by mass, MFR measured at 190°C under a load of 2.16 kg: 0.5 g / 10 min) was used.

[0061] [Styrene-based elastomer (B-2)] As the styrene-based elastomer (B-2), a hydrogenated styrene-butadiene rubber copolymer (product name: "DYNARON1320P", manufactured by ENEOS Material Co., Ltd., polystyrene block content: 10 mass%, MFR measured under conditions of 230°C and 21.2N (load 2.16kg): 3.5g / 10min) was used.

[0062] [Example 1] The 4-methyl-1-pentene polymer (A-1) synthesized above and the styrene elastomer (B-1) were melt-kneaded in a composition ratio of 80 / 20% by mass using a twin-screw extruder (manufactured by Ikegai Co., Ltd., φ=43 mm, L / D=32, cylinder temperature: 260°C) to obtain a 4-methyl-1-pentene resin composition 1. The obtained resin composition 1 was injection molded to prepare a test piece, and the bending modulus and solid viscoelasticity were measured using the test piece. The results are shown in Table 2.

[0063] [Example 2] Except for changing the composition ratio of the 4-methyl-1-pentene polymer (A-1) and the styrene elastomer (B-1) to 60 / 40% by mass, melt kneading was performed in the same manner as in Example 1 to obtain a 4-methyl-1-pentene resin composition 2. The obtained 4-methyl-1-pentene resin composition 2 was injection molded to prepare a test piece, and the flexural modulus and solid viscoelasticity were measured using the test piece. The results are shown in Table 2.

[0064] [Example 3] Except for changing the 4-methyl-1-pentene polymer (A-1) to the 4-methyl-1-pentene polymer (A-2), melt kneading was performed in the same manner as in Example 1 to obtain a 4-methyl-1-pentene resin composition 3. The obtained 4-methyl-1-pentene resin composition 3 was injection molded to prepare a test piece, and the bending modulus and solid viscoelasticity were measured using the test piece. The results are shown in Table 2.

[0065] [Example 4] Except for changing the 4-methyl-1-pentene polymer (A-1) to the 4-methyl-1-pentene polymer (A-2), melt kneading was performed in the same manner as in Example 2 to obtain a 4-methyl-1-pentene resin composition 4. The obtained 4-methyl-1-pentene resin composition 4 was injection molded to prepare a test piece, and the flexural modulus and solid viscoelasticity were measured using the test piece. The results are shown in Table 2.

[0066] [Example 5] The 4-methyl-1-pentene polymer (A-2), the other polymer (C-1) and the styrene elastomer (B-1) were melt-kneaded in a composition ratio of 80 / 10 / 10% by mass using a twin-screw extruder (manufactured by Ikegai Corporation, φ=43 mm, L / D=32, cylinder temperature: 260° C.) to obtain a 4-methyl-1-pentene resin composition 5. The obtained 4-methyl-1-pentene resin composition 5 was injection molded to prepare a test piece, and the flexural modulus and solid viscoelasticity were measured using the test piece. The results are shown in Table 2.

[0067] [Example 6] Except for changing the composition ratio of the 4-methyl-1-pentene polymer (A-2), the other polymer (C-1) and the styrene elastomer (B-1) to 60 / 20 / 20% by mass, melt kneading was performed in the same manner as in Example 5 to obtain a 4-methyl-1-pentene resin composition 6. The obtained 4-methyl-1-pentene resin composition 6 was injection molded to prepare a test piece, and the flexural modulus and solid viscoelasticity were measured using the test piece. The results are shown in Table 2.

[0068] [Comparative Example 1] The 4-methyl-1-pentene polymer (A-1) was injection molded to prepare a test piece, which was then used to measure the flexural modulus and solid viscoelasticity. The results are shown in Table 2.

[0069] [Comparative Example 2] The 4-methyl-1-pentene polymer (A-2) was injection molded to prepare a test piece, which was then used to measure the flexural modulus and solid viscoelasticity. The results are shown in Table 2.

[0070] [Comparative Example 3] Except for changing the composition ratio of the 4-methyl-1-pentene polymer (A-2), the other polymer (C-1) and the styrene elastomer (B-1) to 10 / 80 / 10% by mass, melt kneading was performed in the same manner as in Example 5 to obtain a 4-methyl-1-pentene resin composition 7. The obtained 4-methyl-1-pentene resin composition 7 was subjected to injection molding. The results are shown in Table 2.

[0071] [Comparative Example 4] Except for changing the styrene-based elastomer (B-1) to the styrene-based elastomer (B-2) and changing the composition ratio of the 4-methyl-1-pentene polymer (A-2) and the styrene-based elastomer (B-2) to 50 / 50% by mass, melt kneading was performed in the same manner as in Comparative Example 3 to obtain a 4-methyl-1-pentene resin composition 8. The obtained 4-methyl-1-pentene resin composition 8 was subjected to injection molding. The results are shown in Table 2.

[0072] <Injection moldability> The resin composition obtained above was injection molded using an injection molding machine (model number: M70B, manufactured by Meiki Seisakusho Co., Ltd.) to prepare dumbbell-shaped test pieces conforming to ISO. The case where a test piece could be prepared by injection molding was marked with ◯, and the case where injection molding was not possible or a test piece of the specified size could not be prepared was marked with ×.

[0073] <Flexural modulus> The resin composition obtained above was injection molded using an injection molding machine (model number: M70B, manufactured by Meiki Seisakusho Co., Ltd.) to prepare a test piece for bending test. The obtained test piece for bending test was subjected to a bending test under the following conditions, and the bending modulus at 23°C and -20°C was measured, and the low-temperature impact resistance was evaluated according to the following evaluation criteria. If the bending modulus at -20°C exceeds 2000 MPa, it is hard and difficult to deform, but is brittle and has poor impact resistance, and if the bending modulus at -20°C is 2000 MPa or less, it is easy to deform and has excellent impact resistance. Test piece: 80mm x 10mm x 4mmt Test temperature: 23℃ or -20℃ Test speed: 2mm / min Load cell capacity: 1kN

[0074] -Evaluation criteria for low temperature impact resistance- ◯: The flexural modulus at -20°C is 2000 MPa or less. ×: The bending modulus at −20° C. exceeds 2000 MPa.

[0075] <Solid viscoelasticity> Using a hot press machine (Shinto Metal Industry Co., Ltd., compression molding machine (mold clamping 50 ton)) and a mold: dumbbell shape (distance between chucks: 30 mm, parallel part (width: 5 mm × thickness: 1 mm)), the resin composition obtained above was press molded to prepare test pieces under the conditions of press temperature: 260°C, press pressure: 10 MPa, preheat time: 5 minutes, and press time: 3 minutes. The obtained test pieces were used to measure the solid viscoelasticity in the temperature range of -50°C to 240°C using a solid viscoelasticity measuring device (model number: RSA-III, manufactured by TA Instruments) under the conditions of a chuck distance of 20 mm, a frequency of 1 Hz, a strain of 0.1%, a heating rate of 4°C / min, and a tensile mode. The storage modulus E' at 150°C was calculated, and the heat resistance was evaluated according to the following evaluation criteria. If the storage modulus E' at 150°C is 1.0×10 7 If the thickness is more than this, it can be said that the heat resistance is excellent. -conditions- Deformation mode: Tensile Temperature range: -50℃~240℃ Heating rate: 4℃ / min Frequency: 1Hz

[0076] -Heat resistance evaluation criteria- ○: The storage modulus E' at 150°C is 1.0×10 7 That's all. ×: The storage modulus E' at 150°C is 1.0×10 7 is less than.

[0077] [Table 2]

[0078] In addition, "-" in Table 2 indicates that the corresponding component is not contained or the corresponding evaluation was not performed. It can be seen that the molded articles obtained from the resin compositions of Examples 1 to 6 have excellent impact resistance at low temperatures compared to Comparative Examples 1 and 2. In addition, no injection molded articles were obtained from the resin composition of Comparative Example 3, in which the content of 4-methyl-1-pentene polymer (A) is less than 50 mass% with respect to the total mass of the resin composition, and Comparative Example 4, in which the content of polystyrene blocks in the styrene elastomer is 10 mass%. Therefore, evaluation of low-temperature impact resistance and heat resistance was not performed for Comparative Examples 3 and 4.

Claims

1. A 4-methyl-1-pentene polymer (A) containing a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin having 10 to 20 carbon atoms; a styrene-based elastomer (B) which is a hydrogenated block copolymer of a polystyrene block and a diene block, and the content of the polystyrene block relative to the total mass of the styrene-based elastomer (B) is more than 10 mass% and not more than 50 mass%; Including, The content of the 4-methyl-1-pentene polymer (A) is more than 50 mass% and less than 100 mass% based on the total mass of the resin composition, and the content of the styrene elastomer (B) is 50 mass% or less based on the total mass of the resin composition.

2. The resin composition according to claim 1, wherein the content of the structural units derived from an α-olefin having 10 to 20 carbon atoms in the 4-methyl-1-pentene polymer (A) is 1 to 20 mol % (wherein the total molar number of the structural units derived from the 4-methyl-1-pentene and the structural units derived from an α-olefin having 10 to 20 carbon atoms is 100 mol %).

3. 2. The resin composition according to claim 1, wherein the α-olefin having 10 to 20 carbon atoms is at least one selected from the group consisting of 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene.

4. A molded article comprising the resin composition according to any one of claims 1 to 3.

5. A film comprising the resin composition according to any one of claims 1 to 3.

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