4-methylpentene-based polymer composition and molded article

Abstract

To provide a 4-methyl-1-pentene-based polymer composition with excellent ultraviolet shielding properties even after thermoforming, along with heat and chemical resistance, as well as a molded article obtained from the composition through thermoforming, such as a blow-molded container.SOLUTION: A 4-methyl-1-pentene-based polymer composition (Z) comprises 100 pts.wt. of a 4-methyl-1-pentene-based polymer (X) and 0.05-0.5 pt.wt. of a benzotriazole-based ultraviolet absorber (Y), where the benzotriazole-based ultraviolet absorber (Y) exhibits a mass loss of 1% or less as determined by TGA analysis (under atmospheric conditions, 280°C).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a 4-methyl-pentene polymer composition having excellent ultraviolet shielding properties and a molded article such as a bottle. [Background technology]

[0002] Resin compositions made of 4-methyl-1-pentene polymers are used in various molded products. Depending on the application, improvements in heat resistance and prevention of deterioration due to light are required, and various improvements have been made. For example, molded articles made from these resin compositions are prone to decomposition and deterioration due to heat history, and therefore heat stabilizers are added thereto. Further, radicals generated by light or heat are absorbed by a heat stabilizer, and the heat stabilizer is consumed, thereby preventing deterioration of the resin.

[0003] Furthermore, molded articles of 4-methyl-1-pentene polymers have the potential to be used in reagent bottles due to their excellent heat resistance and chemical resistance, and there is a demand for them to be able to block ultraviolet rays in order to protect the chemicals contained therein. 2. Description of the Related Art Molded articles obtained by blending a 4-methyl-1-pentene polymer with an ultraviolet absorber and melt molding the resulting mixture are known (Patent Document 1).

[0004] [Patent Document 1] JP 2012-36270 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have investigated the ultraviolet ray shielding properties of 4-methyl-1-pentene polymer molded articles, but found that the ultraviolet ray shielding properties of the molded articles were insufficient due to thermal decomposition of the ultraviolet ray absorbent blended during thermoforming. [Means for solving the problem]

[0006] The present invention relates to a 4-methyl-1-pentene polymer composition having excellent ultraviolet shielding properties, and the embodiments of the present invention include the following [1] to [8].

[0007] [1] 4-methyl-1-pentene polymer (X) 100 parts by weight, 0.05 to 0.5 parts by weight of a benzotriazole-based ultraviolet absorber (Y), The 4-methyl-1-pentene polymer composition (Z) has a mass loss of 1% or less as determined by TGA analysis (atmospheric conditions, 280° C.) of the benzotriazole ultraviolet absorber (Y). [2] 4-methyl-1-pentene polymer (X) 100 parts by weight, 0.05 to 0.5 parts by weight of a benzotriazole-based ultraviolet absorber (Y), The 4-methyl-1-pentene polymer composition (Z) is characterized in that the benzotriazole ultraviolet absorber (Y) contains two or more benzotriazoles in one molecule. [3] The 4-methyl-1-pentene polymer composition (Z) according to the above item [1], wherein the benzotriazole ultraviolet absorber (Y) contains two or more benzotriazoles in one molecule. [4] The 4-methyl-1-pentene polymer composition (Z) according to any one of the above [1] to [3], wherein the benzotriazole ultraviolet absorber (Y) is represented by the following general formula (1):

[0008] [ka] In the general formula (1), R 1 , R 4 may be the same or different, and each represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, R 5 SO- group or R 5 It is an O2-group. R 2 , R 3may be the same or different, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a COOH group, a phenyl group, a phenylalkyl group containing 1 to 4 carbon atoms in the alkyl moiety, or a cycloalkyl group having 5 to 8 carbon atoms. R 5 is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group substituted by an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, or the above aryl groups substituted by one or two alkyl groups having 1 to 4 carbon atoms, or a 1,1,2,2-tetrahydroperfluoroalkyl group (the perfluoroalkyl portion of this group consists of 6 to 16 carbon atoms). R 1 and R 4 are preferably the same, and R 2 and R 3 are preferably the same. [5] The 4-methyl-1-pentene polymer composition (Z) according to any one of [1] to [4] above, wherein the benzotriazole ultraviolet absorber (Y) is 2,2'-methylene-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol. [6] 4-methyl-1-pentene polymer (X) 15 to 40% by mass of 4-methyl-1-pentene copolymer (A), 40 to 80% by mass of 4-methyl-1-pentene copolymer (B), and 4-Methyl-1-pentene copolymer (C) 5 to 30% by mass The 4-methyl-1-pentene polymer composition (Z) according to any one of the above [1] to [5], which comprises: (The total of copolymer (A), copolymer (B) and copolymer (C) is 100% by mass.) The 4-methyl-1-pentene copolymer (A) satisfies the following requirements (Ai) and (A-ii). Requirements (Ai): The structural unit (i) derived from 4-methyl-1-pentene 97.5 to 100 mol% Ethylene and α-olefins with 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 2.5 to 0 mol% (However, the total of the structural units (i) and (ii) is 100 mol %). Requirement (A-ii): Intrinsic viscosity [η] A (135℃, decalin) is 1.0~5.0dl / g. The 4-methyl-1-pentene copolymer (B) satisfies the following requirements (Bi) to (B-iii). Requirements(Bi): The structural unit (i) derived from 4-methyl-1-pentene 91.0 to 97.5 mol% Ethylene and α-olefins with 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 9.0 to 2.5 mol% (However, the total of the structural units (i) and (ii) is 100 mol %). Requirement (B-ii): Intrinsic viscosity [η] B (135℃, decalin) is 2.0~5.0dl / g. Requirement (B-iii): The melting point (Tm) (measured by DSC) is less than 180°C. The 4-methyl-1-pentene copolymer (C) satisfies the following requirements (Ci) to (C-iii). Requirements(Ci): The structural unit (i) derived from 4-methyl-1-pentene 50 to 91.0 mol% Ethylene and α-olefins with 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 50 to 9.0 mol% (However, the total of the structural units (i) and (ii) is 100 mol %). Requirement (C-ii): Intrinsic viscosity [η] C (135℃, decalin) is 2.0~5.0dl / g. Requirement (C-iii): No melting point (Tm) (measured by DSC) was observed. [7] A molded article obtained by molding the 4-methyl-1-pentene polymer composition (Z) according to any one of the above [1] to [6]. [8] A blown container obtained by molding the 4-methyl-1-pentene polymer composition (Z) according to any one of the above [1] to [6]. Effect of the Invention

[0009] According to the present disclosure, it is possible to provide a resin composition containing a 4-methyl-1-pentene polymer and a specific ultraviolet absorber, and further to provide a molded article thermoformed using the resin composition, the molded article having excellent heat resistance and chemical resistance and excellent ultraviolet shielding properties.

[0010] <Benzotriazole-based UV absorber (Y)> In one embodiment of the present invention, the benzotriazole-based ultraviolet absorber (Y) is selected from compounds whose mass loss by TGA analysis (atmospheric conditions, 280° C.) is 1% or less. In another embodiment of the present invention, the benzotriazole-based ultraviolet absorber (Y) is selected from compounds containing two or more benzotriazoles in one molecule. In a preferred embodiment of the present invention, the benzotriazole-based ultraviolet absorber (Y) is selected from compounds whose mass loss by TGA analysis (atmospheric conditions, 280°C) is 1% or less and which contain two or more benzotriazoles in one molecule. In these embodiments, the benzotriazole-based ultraviolet absorber (Y) is preferably a compound represented by the following general formula (1).

[0011] [ka] In the general formula (1), R 1 , R 4 may be the same or different, and each represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, R 5 SO- group or R 5 It is an O2-group. R 2 , R 3 may be the same or different, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a COOH group, a phenyl group, a phenylalkyl group containing 1 to 4 carbon atoms in the alkyl moiety, or a cycloalkyl group having 5 to 8 carbon atoms. R 5 is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group substituted by an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, or the above aryl groups substituted by one or two alkyl groups having 1 to 4 carbon atoms, or a 1,1,2,2-tetrahydroperfluoroalkyl group (the perfluoroalkyl portion of this group consists of 6 to 16 carbon atoms). R 1 and R 4 are preferably the same, and R 2 and R 3 are preferably the same. Specific examples of the benzotriazole-based ultraviolet absorber (Y) used in the present invention include: 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)- 4-(1,1,3,3-tetramethylbutyl)phenol], (Tinuvin360: Registered trademark; BASF Japan Ltd.) is most preferred. The blending ratio of benzotriazole-based ultraviolet absorber (Y) is: Relative to 100 parts by weight of the 4-methyl-1-pentene polymer (X), The benzotriazole-based ultraviolet absorber (Y) is 0.05 to 0.5 parts by weight. The following are known as benzotriazole-based ultraviolet absorbents, but they are insufficient in heat resistance, and the ultraviolet shielding properties of the molded products obtained by thermoforming them in combination with 4-methyl-1-pentene polymer (X) are insufficient. 2-(2H-benzotriazol-2-yl)- 4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)- 4-(1,1,3,3-tetramethylbutyl)phenol, 2-(5-chloro-2H-benzotriazol-2-yl)- 6-tert-butyl-4-methylphenol, (BASF Japan Ltd., TINUVIN326) 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2′-hydroxy-5′-t-octylphenyl)benzotriazole (BASF Japan Ltd., TINUVIN329)

[0012] <4-methyl-1-pentene polymer (X)> The 4-methyl-1-pentene polymer (X) used in the present invention is a homopolymer consisting of a structural unit (i) derived from 4-methyl-1-pentene, or a copolymer containing the structural unit (i) together with a comonomer, for example, a structural unit (ii) derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).

[0013] Here, examples of the α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene. As the structural unit (ii), from the viewpoint of obtaining a polymer composition with good moldability, among ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), α-olefins having 10 to 20 carbon atoms are preferred, and α-olefins having 10 to 18 carbon atoms are more preferred. Specifically, 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred. Also, for example, it is preferred to use 1-hexadecene and 1-octadecene in combination.

[0014] The 4-methyl-1-pentene polymer (X) may have only one type or two or more types of structural units derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene). The 4-methyl-1-pentene polymer (X) usually comprises 85 to 100 mol % of the structural unit (i) and 15 to 0 mol % of the structural unit (ii). (However, the total of the structural units (i) and (ii) is 100 mol %).

[0015] Furthermore, the 4-methyl-1-pentene polymer (X) may further have a structural unit derived from another polymerizable compound other than the structural unit (ii) consisting of 4-methyl-1-pentene, ethylene, and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), within a range that does not impair the object of the present invention. Examples of the other polymerizable compound include 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, 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-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene.

[0016] The various monomers disclosed in the present invention may be derived from fossil raw materials or biomass.

[0017] In the 4-methyl-1-pentene copolymer (X), 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, based on 100 mol % of all structural units constituting the 4-methyl-1-pentene copolymer.

[0018] <Characteristics of 4-methyl-1-pentene polymer (X)> In order for the 4-methyl-1-pentene polymer (X) to have excellent physical properties such as heat resistance, transparency, light weight, releasability, and stain resistance, it is desirable for it to satisfy the following requirements (Xi), (X-ii), and (X-iii).

[0019] Requirements(Xi): The structural unit (i) derived from 4-methyl-1-pentene 90.0 to 96.0 mol% Ethylene and α-olefins with 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 10.0 to 4.0 mol% (However, the total of the structural units (i) and (ii) is 100 mol %). Requirement (X-ii): Intrinsic viscosity [η] X (135℃, decalin) is 1.8~4.0dl / g. Requirements (X-iii): The melting point (Tm) (measured by DSC) is less than 240°C.

[0020] In order to obtain excellent physical properties, the polymer (X) used in the present invention is a 4-methyl-1-pentene copolymer (A) (hereinafter also referred to as "copolymer (A)"), 4-methyl-1-pentene copolymer (B) (hereinafter also referred to as "copolymer (B)"); and 4-Methyl-1-pentene copolymer (C) (hereinafter also referred to as "copolymer (C)") and each of which preferably satisfies the following:

[0021] 15 to 40% by mass of 4-methyl-1-pentene copolymer (A), 40 to 80% by mass of 4-methyl-1-pentene copolymer (B), and 4-Methyl-1-pentene copolymer (C) 5 to 30% by mass It is desirable for each of these to meet the following requirements. (The total of copolymer (A), copolymer (B) and copolymer (C) is taken as 100 mass %).

[0022] The 4-methyl-1-pentene copolymer (A) satisfies the following requirements (Ai) and (A-ii). Requirements (Ai): The structural unit (i) derived from 4-methyl-1-pentene 97.5 to 100 mol% Ethylene and α-olefins with 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 2.5 to 0 mol% (However, the total of the structural units (i) and (ii) is 100 mol %). Requirement (A-ii): Intrinsic viscosity [η] A (135℃, decalin) is 1.0~5.0dl / g.

[0023] The 4-methyl-1-pentene copolymer (B) satisfies the following requirements (Bi) to (B-iii). Requirements(Bi): The structural unit (i) derived from 4-methyl-1-pentene 91.0 to 97.5 mol% Ethylene and α-olefins with 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 9.0 to 2.5 mol% (However, the total of the structural units (i) and (ii) is 100 mol %). Requirement (B-ii): Intrinsic viscosity [η] B (135℃, decalin) is 2.0~5.0dl / g. Requirement (B-iii): The melting point (Tm) (measured by DSC) is less than 180°C.

[0024] The 4-methyl-1-pentene copolymer (C) satisfies the following requirements (Ci) to (C-iii). Requirements(Ci): The structural unit (i) derived from 4-methyl-1-pentene 50 to 91.0 mol% Ethylene and α-olefins with 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 50 to 9.0 mol% (However, the total of the structural units (i) and (ii) is 100 mol %). Requirement (C-ii): Intrinsic viscosity [η] C (135℃, decalin) is 2.0~5.0dl / g. Requirement (C-iii): No melting point (Tm) (measured by DSC) was observed.

[0025] Each of the copolymers is described below. <4-methyl-1-pentene copolymer (A)> The copolymer (A) may contain only one type of copolymer, or may contain two or more types of copolymers. When the copolymer (A) contains two or more types of copolymers, each copolymer may satisfy the above requirements (Ai) and (A-ii), or the copolymer as a whole may satisfy the above requirements (Ai) and (A-ii).

[0026] Requirement (Ai) is as described above, and the content of structural units (i) derived from 4-methyl-1-pentene is 97.5 mol% or more and less than 100 mol%, 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 more than 0 mol% and 2.5 mol% or less, provided that 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 100 mol%.

[0027] Examples of the α-olefins (excluding 4-methyl-1-pentene) having 3 to 20 carbon atoms in the structural unit (ii) include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene. As the structural unit (ii), from the viewpoint of obtaining a polymer composition with good moldability, among ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), α-olefins having 10 to 20 carbon atoms are preferred, and α-olefins having 10 to 18 carbon atoms are more preferred. Specifically, 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred. Also, for example, it is preferred to use 1-hexadecene and 1-octadecene in combination.

[0028] The content of the structural unit (i) derived from 4-methyl-1-pentene is more preferably 97.5 to 99.5 mol%, and even more preferably 97.7 to 99.0 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 2.5 mol%, and even more preferably 1.0 to 2.3 mol%.

[0029] In the copolymer (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 are within the above-mentioned ranges, a polymer composition with good moldability can be obtained. The requirement (A-ii) is as described above, and the intrinsic viscosity [η] measured in decalin at 135 ° C. A is 1.0 to 5.0 dl / g, and preferably 1.0 to 4.0 dl / g.

[0030] <4-methyl-1-pentene copolymer (B)> The copolymer (B) may contain only one type of copolymer, or may contain two or more types of copolymers. When the copolymer (B) contains two or more types of copolymers, each copolymer may satisfy the above requirements (Bi) and (B-ii), or the copolymer as a whole may satisfy the above requirements (Bi) and (B-ii).

[0031] Requirement (Bi) is as described above, and the content of structural units (i) derived from 4-methyl-1-pentene is 91.0 mol% or more and less than 97.5 mol%, 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 more than 0 mol% and 2.5 mol% or less, provided that the sum 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 100 mol%.

[0032] Examples of the α-olefins (excluding 4-methyl-1-pentene) having 3 to 20 carbon atoms in the structural unit (ii) include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene. As the structural unit (ii), from the viewpoint of obtaining a polymer composition with good moldability, among ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), α-olefins having 10 to 20 carbon atoms are preferred, and α-olefins having 10 to 18 carbon atoms are more preferred. Specifically, 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred. Also, for example, it is preferred to use 1-hexadecene and 1-octadecene in combination.

[0033] The content of the structural unit (i) derived from 4-methyl-1-pentene is more preferably 91.5 to 96.0 mol%, and even more preferably 91.5 to 95.0 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 8.5 to 4.0 mol%, and even more preferably 8.5 to 5.0 mol%.

[0034] 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 are within the above-mentioned ranges, a polymer composition with good moldability can be obtained. Requirement (B-ii) is as described above, and the intrinsic viscosity [η] measured in decalin at 135 ° C. B is 2.0 to 5.0 dl / g, and preferably 2.2 to 4.5 dl / g.

[0035] The requirement (B-iii) is as described above, and the melting point (Tm) measured by DSC is less than 180°C, preferably less than 175°C.

[0036] <4-methyl-1-pentene copolymer (C)> The copolymer (C) may contain only one type of copolymer, or may contain two or more types of copolymers. When the copolymer (C) contains two or more types of copolymers, each copolymer may satisfy the above requirement (Ci) and requirement (C-ii), or the copolymer as a whole may satisfy the above requirement (Ci) and requirement (C-ii).

[0037] Requirement (Ci) is as described above, and the content of structural units (i) derived from 4-methyl-1-pentene is 50 mol% or more and less than 91.0 mol%, 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 50 mol% or more and 9.0 mol% or less. However, 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 100 mol%.

[0038] Examples of the α-olefins (excluding 4-methyl-1-pentene) having 3 to 20 carbon atoms in the structural unit (ii) include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene. As the structural unit (ii), from the viewpoint of obtaining a polymer composition with good moldability, among ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), α-olefins having 10 to 20 carbon atoms are preferred, and α-olefins having 10 to 18 carbon atoms are more preferred. Specifically, 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred. Also, for example, it is preferred to use 1-hexadecene and 1-octadecene in combination.

[0039] The content of the structural unit (i) derived from 4-methyl-1-pentene is more preferably 60 to 90.0 mol%, and even more preferably 70 to 89.0 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 40 to 10.0 mol%, and even more preferably 30 to 11.0 mol%.

[0040] 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 are within the above-mentioned ranges, a polymer composition with good moldability can be obtained.

[0041] Requirement (C-ii) is as described above, and the intrinsic viscosity [η] measured in decalin at 135 ° C. C is 2.0 to 5.0 dl / g, and preferably 2.5 to 4.5 dl / g.

[0042] The requirement (C-iii) is as described above, and the melting point (Tm) measured by DSC is not observed.

[0043] <Ratio of amounts of copolymer (A), copolymer (B) and copolymer (C)> The content of copolymer (A) in the 4-methyl-1-pentene polymer (X) is preferably 15 to 40 mass%, more preferably 17 to 38 mass%, the content of copolymer (B) is preferably 40 to 80 mass%, more preferably 45 to 75 mass%, and the content of copolymer (C) is preferably 5 to 30 mass%, more preferably 1025 mass%, where the total of copolymer (A), copolymer (B) and copolymer (C) is 100 mass%.

[0044] The polymer (X) contains the copolymer (A), the copolymer (B) and the copolymer (C) in the above-mentioned ratio, and thus has excellent stretchability and good moldability.

[0045] <Method for producing 4-methyl-1-pentene polymer (X)> The 4-methyl-1-pentene polymer (X), as well as the above-mentioned copolymers (A), (B) and (C), can be obtained by, for example, polymerizing 4-methyl-1-pentene alone, or polymerizing it with a linear α-olefin having 2 to 20 carbon atoms, and further, if necessary, with the above-mentioned other polymerizable compounds. By carrying out this polymerization in the presence of a metallocene catalyst, the above-mentioned 4-methyl-1-pentene polymer (Z), copolymer (A), copolymer (B) and copolymer (C) can be suitably obtained.

[0046] Examples of the metallocene catalyst include those described in WO 01 / 53369, WO 01 / 27124, JP 03-193796 A, JP 02-41303 A, WO 06 / 025540 A or WO 2013 / 099876 A.

[0047] The metallocene catalyst may, for example, be a catalyst composed of at least a metallocene compound (a) and a support (b).

[0048] Metallocene compound (a) The metallocene compound (a) is represented, for example, by general formula (1) or general formula (2).

[0049] [ka]

[0050] The meanings of each symbol in general formula (1) or general formula (2) are as follows. R 1 ~R 14 R is independently a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, or a silicon-containing group. 1 From R 4 Adjacent substituents up to may be bonded together to form a ring. 5 From R 12 Adjacent substituents up to may be bonded to each other to form a ring.

[0051] Y is a carbon atom or a silicon atom. A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond and / or an aromatic ring. A may contain two or more ring structures including the ring formed together with Y.

[0052] M is a metal (transition metal) selected from Group 4 of the periodic table, and examples thereof include titanium, zirconium, and hafnium. Q is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons. When j is 2 or more, each Q may be the same or different. j is an integer of 1 to 4, and preferably 2.

[0053] R 1 ~R 14 Examples of the hydrocarbon group in the formula include hydrocarbon groups having 1 to 20 carbon atoms, and specific examples thereof include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkylaryl groups having 7 to 20 carbon atoms.

[0054] R 1 ~R 14 The substituted hydrocarbon group (excluding silicon-containing groups) in the above formula (I) is a group in which some or all of the hydrogen atoms contained in the hydrocarbon group have been substituted with functional groups such as halogen atoms (fluorine, chlorine, bromine, iodine), hydroxyl groups, and amino groups.

[0055] R 1 ~R 14 Examples of the silicon-containing group in the formula (I) include alkylsilyl groups or arylsilyl groups having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, and triphenylsilyl.

[0056] R on the fluorene ring 5 From R 12Adjacent substituents up to may be bonded to each other to form a ring. Such substituted fluorenyl groups include, for example, benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, and octamethyloctahydrodibenzofluorenyl.

[0057] R on the fluorene ring 5 From R 12 The substituents are symmetrical for ease of synthesis, i.e., R 5 =R 12 , R 6 =R 12 , R 7 =R 10 , R 8 =R 9 The fluorene ring portion is preferably unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. The 3-, 6-, 2- and 7-positions on the fluorene ring are preferably R 7 , R 10 , R 6 , R 11 Corresponds to. R 13 and R 14 are preferably each independently a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group.

[0058] In the case of general formula (1), R 13 and R 14 is bonded to Y to form a substituted methylene group or a substituted silylene group as a bridging moiety. Specific examples of the substituted methylene group and the substituted silylene group include, for example, dialkylmethylene, dicycloalkylmethylene, alkylcycloalkylmethylene, alkylarylmethylene, diarylmethylene, dialkylsilylene, dicycloalkylsilylene, alkylcycloalkylsilylene, alkylarylsilylene, diarylsilylene, and halogenated groups thereof.

[0059] In the case of general formula (2), Y bonds to the divalent hydrocarbon group A to form a cycloalkylidene group or a cyclomethylenesilylene group, etc. Specific examples of the cycloalkylidene group and the cyclomethylenesilylene group include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo[3.3.1]nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanylidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, and cycloheptamethylenesilylene.

[0060] In Q, examples of the halogen atom include fluorine, chlorine, bromine, and iodine; examples of the hydrocarbon group having 1 to 20 carbon atoms include R 1 ~R 14 Examples of the anionic ligand include an alkoxy group, an aryloxy group, a carboxylate group, a sulfonate group, etc. Examples of the neutral ligand capable of coordinating with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, etc., and ethers such as tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, etc. At least one of Q is preferably a halogen atom or an alkyl group having 1 to 20 carbon atoms.

[0061] Specific examples of the metallocene compound (a) include the compounds exemplified in WO 01 / 27124, WO 2006 / 025540, or WO 2007 / 308607.

[0062] The metallocene compound (a) is particularly preferably a compound represented by the general formula [A2] described in WO 2014 / 050817, etc.

[0063] [ka]

[0064] In formula [A2], R 1b is a hydrocarbon group, a silicon-containing group, or a halogen-containing hydrocarbon group; R 2b ~R 12b are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group, and may be the same or different, and each substituent may be bonded to each other to form a ring. M is a transition metal of Group 4 of the periodic table, n is an integer of 1 to 3, Q is the same as Q in the general formula (1) or (2), and j is an integer of 1 to 4.

[0065] R 1b From R 12b Examples of the hydrocarbon group in include linear hydrocarbon groups such as linear alkyl groups and linear alkenyl groups; branched hydrocarbon groups such as branched alkyl groups; cyclic saturated hydrocarbon groups such as cycloalkyl groups, norbornyl groups and adamantyl groups; cyclic unsaturated hydrocarbon groups such as aryl groups and cycloalkenyl groups; and groups in which one or more hydrogen atoms of a saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group, such as an aralkyl group. The number of carbon atoms in the hydrocarbon group is usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10.

[0066] R 1b From R 12b Examples of the silicon-containing group in the formula include a group represented by the formula -SiR3 (wherein each of the multiple R's is independently an alkyl group having 1 to 15 carbon atoms or a phenyl group).

[0067] R 1b From R 12b Examples of the halogen-containing hydrocarbon group in the above formula include groups in which one or more hydrogen atoms of the above hydrocarbon group are substituted with halogen atoms, such as a trifluoromethyl group.

[0068] R 2b From R 12b Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0069] In formula [A2], the ring (spiro ring, additional ring) formed by bonding two substituents to each other may be, for example, an alicyclic ring or an aromatic ring.Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, and a cyclopentene ring, and preferably a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring.In addition, such a ring structure may further have a substituent such as an alkyl group on the ring.

[0070] R 1b It is particularly preferable that R is a substituent in which the carbon having a free valence (the carbon bonded to the cyclopentadienyl ring) is a tertiary carbon. 1b Specific examples of the alkyl group include a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group.

[0071] The fluorene ring portion is not particularly limited as long as it has a structure obtained from a known fluorene derivative. 4b and R 5b From the viewpoint of molecular weight, is preferably a hydrogen atom.

[0072] R 2b , R 3b , R 6b and R 7b is preferably a hydrocarbon group having 1 to 20 carbon atoms. 2b and R 3b are bonded to each other to form a ring, and R 6b and R 7bmay be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl, 1,1,3,3,6,6,8,8-octamethyl-2,3,6,7,8,10-hexahydro-1H-dicyclopenta[b,h]fluorenyl, and 1',1',3',6',8',8'-hexamethyl-1'H,8'H-dicyclopenta[b,h]fluorenyl.

[0073] R 8b is preferably a hydrogen atom. 9b is preferably an alkyl group having 2 or more carbon atoms. From the viewpoint of synthesis, R 10b and R 11b It is also preferred that is a hydrogen atom.

[0074] Alternatively, if n=1, R 9b and R 10b are more preferably bonded to each other to form a ring, and the ring is particularly preferably a six-membered ring such as a cyclohexane ring. In this case, R 11b is preferably a hydrogen atom. R 12b is preferably an alkyl group.

[0075] M is a transition metal of Group 4 of the periodic table, for example, Ti, Zr or Hf, preferably Zr or Hf, and particularly preferably Zr.

[0076] n is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. Having n be within the above range is preferred from the viewpoint of efficiently obtaining the produced polymer. j is an integer of 1 to 4, and is preferably 2.

[0077] As the compound represented by the general formula [A2], (8-octamethylfluorene-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride or (8-(2,3,6,7-tetramethylfluorene)-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride is particularly preferred. Here, the above-mentioned octamethylfluorene refers to 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene.

[0078] Carrier (b) The support (b) is preferably in the form of particles, and the metallocene compound (a) is immobilized on the surface and inside of the support (b) to form the metallocene catalyst. A catalyst in this form is generally called a supported metallocene catalyst.

[0079] The carrier (b) is mainly composed of an organoaluminum compound (b-1), an organoboron compound (b-2), an inorganic compound (b-3), or a complex of two or more of these compounds. do. Examples of the organoaluminum compound (b-1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-normal octylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, tricycloalkylaluminum, and organoaluminum oxy compounds such as aluminoxane. Examples of the organoaluminum compound (b-1) include organoaluminum oxy compounds containing boron atoms, halogen-containing aluminoxanes as exemplified in WO 2005 / 066191 and WO 2007 / 131010, and ionic aluminoxanes as exemplified in WO 2003 / 082879.

[0080] Examples of the organic boron compound (b-2) include trialkylammonium tetraarylborate, trialkylammonium tetra(aryl halide)borate, dioctadecylmethylammonium tetraarylborate, dioctadecylmethylammonium tetra(aryl halide)borate, N,N-dialkylanilinium tetraarylborate, and N,N-dialkylanilinium tetra(aryl halide)borate.

[0081] Examples of the inorganic compound (b-3) include porous oxides, inorganic halides, clays, clay minerals, and ion-exchangeable layered compounds. Examples of the porous oxides include oxides such as SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, and ThO2, or composites or mixtures containing these. Examples of the oxides include natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, and SiO2-TiO2-MgO. Examples of the inorganic halides include MgCl2, MgBr2, MnCl2, and MgBr2. The inorganic halides may be used as they are, or may be used after being pulverized by a ball mill or a vibration mill. In addition, the inorganic halides may be dissolved in a solvent such as alcohol, and then precipitated into fine particles by a precipitating agent.

[0082] From the viewpoint of high activity and further suppressing the amount of solvent-soluble matter, the support (b) is preferably a support containing aluminum atoms. The content of aluminum atoms in the support (b) is preferably 20 mass% or more, more preferably 20 to 60 mass%, further preferably 30 to 50 mass%, and particularly preferably 35 to 47 mass%.

[0083] As such a carrier (b), a solid aluminoxane is preferably used, and for example, the solid aluminoxanes disclosed in WO 2010 / 055652, WO 2013 / 146337, or WO 2014 / 123212 are particularly preferably used.

[0084] The term "solid" means that the solid aluminoxane is substantially maintained in a solid state in the reaction environment in which it is used. More specifically, it means that the aluminoxane is in a solid state in an inert hydrocarbon medium such as hexane or toluene used in the reaction when preparing an olefin polymerization solid catalyst component by contacting each component constituting the olefin polymerization catalyst under a specific temperature and pressure environment.

[0085] The solid aluminoxane preferably contains an aluminoxane having at least one type of constituent unit selected from the constituent units represented by the following formula (1) and the constituent units represented by the following formula (2), more preferably contains an aluminoxane having a constituent unit represented by the following formula (1), and even more preferably contains a polymethylaluminoxane consisting only of the constituent units represented by the following formula (1).

[0086] [ka]

[0087] In formula (1), Me is a methyl group. In formula (2), R 1 is a hydrocarbon group having 2 to 20 carbon atoms, preferably a hydrocarbon group having 2 to 15 carbon atoms, more preferably a hydrocarbon group having 2 to 10 carbon atoms. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, and an aryl group.

[0088] The structure of solid aluminoxane is not necessarily clear, and is generally assumed to have a structure in which the structural units represented by formula (1) and / or formula (2) are repeated about 2 to 50 times, but is not limited to this structure. The bonding form of the structural units is various, for example, linear, cyclic, or cluster-like, and the aluminoxane is generally assumed to be one of these, or a mixture of these. The aluminoxane may also be composed of only the structural units represented by formula (1) or formula (2).

[0089] As the solid aluminoxane, solid polymethylaluminoxane is preferable, and solid polymethylaluminoxane consisting only of the constitutional unit represented by formula (1) is more preferable. The solid aluminoxane functions as a catalyst support. In addition to the solid aluminoxane, it is not necessary to use a solid inorganic support such as silica, alumina, silica-alumina, magnesium chloride, or a solid organic support such as polystyrene beads as a catalyst support. Solid aluminoxanes can be prepared, for example, by the methods described in WO 2010 / 055652 and WO 2014 / 123212.

[0090] 《Organic compound component (c)》 The metallocene catalyst may further contain an organic compound component (c) as required. The organic compound component (c) is used for the purpose of improving the polymerization performance and the physical properties of the resulting polymer as required. As the organic compound component (c), the above-mentioned organoaluminum compound (b-1) may be used. Other examples include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0091] Polymerization Conditions 4-methyl-1-pentene polymer (X), copolymer (A), copolymer (B ), and to obtain the copolymer (C), polymerization of 4-methyl-1-pentene, or further ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods. In the liquid phase polymerization method, an inert hydrocarbon solvent can be used, and specifically, examples of the solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane; and mixed solvents of two or more selected from the above. In addition, the olefins themselves including 4-methyl-1-pentene can be used as the polymerization solvent.

[0092] In the above-mentioned polymerization, the method of use and the order of addition of each component can be selected arbitrarily, but the following method is exemplified. Hereinafter, the metallocene compound (a), the carrier (b) and the organic compound component (c) are also referred to as "components (a) to (c)", respectively. (a) A method in which components (a) and (b) are added to a polymerization reactor in any order. (b) A catalyst component in which component (a) is supported on component (b) is added to a polymerization vessel.

[0093] In each of the above methods (a) and (b), component (c) may be further added at any stage. At least two of the catalyst components may be in contact with each other in advance. In the solid catalyst component in which component (a) is supported on component (b), an olefin such as 4-methyl-1-pentene or 3-methyl-1-pentene may be prepolymerized, or a further catalyst component may be supported on the prepolymerized solid catalyst component.

[0094] When a monomer such as 4-methyl-1-pentene is polymerized using a metallocene catalyst, the amount of each component that can constitute the metallocene catalyst is as follows. In addition, the content of each component in the metallocene catalyst can be adjusted as follows.

[0095] Component (a) is usually used in an amount of 10 -10 ~10 -2 Molar, preferably 10 -8 ~10 ―3 The component (b-1) can be used in an amount such that the molar ratio [Al / M] of aluminum atoms in the component (b-1) to the total transition metal atoms (M) in the component (a) is usually 10 to 10,000, preferably 30 to 2,000, and particularly preferably 150 to 500. The component (b-2) can be used in an amount such that the molar ratio [(b-2) / M] of component (b-2) to the total transition metal atoms (M) in the component (a) is usually 10 to 10,000, preferably 30 to 2,000, and more preferably 150 to 500. The component (b-3) can be used in an amount such that the molar ratio [(b-3) / M] of component (b-3) to the total transition metal atoms (M) in the component (a) is usually 10 to 10,000, preferably 30 to 2,000, and more preferably 150 to 500.

[0096] When component (c) is used, when component (b) is component (b-1), it can be used in an amount such that the molar ratio of aluminum atoms in component (b-1) to component (c) [Al / (c)] is usually 0.002 to 500, preferably 0.01 to 60. When component (b) is component (b-2), it can be used in an amount such that the molar ratio of component (b-2) to component (c) [(b-2) / (c)] is usually 0.002 to 500, preferably 0.01 to 60. When component (b) is component (b-3), it can be used in an amount such that the molar ratio of component (b-3) to component (c) [(b-3) / (c)] is usually 0.002 to 500, preferably 0.01 to 60.

[0097] The polymerization temperature is usually -50 to 200°C, preferably 0 to 100°C, more preferably 20 to 100°C. The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. For the purpose of controlling the molecular weight or polymerization activity of the produced polymer, hydrogen can be added to the polymerization system, and the amount of hydrogen added is appropriately about 0.001 to 100 NL per kg of olefin.

[0098] As for the polymerization conditions, it is also possible to adopt multi-stage polymerization in which polymerization is performed in two or more stages with different reaction conditions. For example, by carrying out polymerization stepwise under two conditions with different amounts of hydrogen used, or different ratios of 4-methyl-1-pentene, or further ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), it is possible to obtain a polymer with a desired molecular weight distribution or composition distribution.

[0099] For example, the mixture of copolymers (A), (B), and (C) can be produced by a multi-stage polymerization method including a step (1) of producing 4-methyl-1-pentene copolymer (A) by slurry polymerization, a step (2) of producing 4-methyl-1-pentene copolymer (B) by slurry polymerization in the presence of copolymer (A) obtained in step (1) such that the amount of copolymer (B) is a desired mass% when the total amount of copolymer (A) and copolymer (B) is 100 mass%, and a step (3) of producing 4-methyl-1-pentene copolymer (C) by slurry polymerization in the presence of copolymer (A) and copolymer (B) obtained in step (2) such that the amount of copolymer (C) is a desired mass% when the total amount of copolymer (A), copolymer (B), and copolymer (C) is 100 mass%.

[0100] The multi-stage polymerization method has steps (1), (2) and (3) which are different in polymerization conditions, and may be a four-stage or more polymerization method further including other steps in addition to steps (1), (2) and (3), if necessary.

[0101] 《Process (1)》 In step (1), the 4-methyl-1-pentene copolymer (A) is produced by slurry polymerization. In step (1), the ratio of 4-methyl-1-pentene to at least one monomer selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is set so that the amount of the structural units derived from each is within the above-mentioned range.

[0102] In the step (1), a slurry containing the copolymer (A) is obtained. The slurry concentration, that is, the concentration of the copolymer (A) particles is usually 0.015 to 45% by mass, and preferably 0.03 to 35% by mass.

[0103] 《Process (2)》 In step (2), 4-methyl-1-pentene copolymer (B) is produced by slurry polymerization in the presence of copolymer (A) obtained in step (1). In step (2), the feed ratio of 4-methyl-1-pentene to at least one monomer selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is set so that the amount of each of the constituent units derived from each of them is within the above-mentioned range.

[0104] In step (2), copolymer (B) is produced so that the amount of copolymer (B) is a desired mass %, assuming that the total amount of copolymer (A) obtained in step (1) and copolymer (B) obtained in step (2) is 100 mass %.

[0105] In one embodiment of the step (2), 4-methyl-1-pentene and at least one monomer selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) are added to a slurry containing the copolymer (A), and slurry polymerization of these monomers is carried out.

[0106] In the step (2), a slurry containing particles containing the copolymer (A) and the copolymer (B) is obtained. The slurry concentration, i.e., the particle concentration, is usually 3 to 50 mass %, preferably 5 to 40 mass %.

[0107] 《Process (3)》 In step (3), 4-methyl-1-pentene copolymer (C) is produced by slurry polymerization in the presence of copolymer (A) and copolymer (B) obtained in step (2). In step (3), the feed ratio of 4-methyl-1-pentene to at least one monomer selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is set so that the amount of each of the constituent units derived from each of them is within the above-mentioned range.

[0108] In step (3), copolymer (C) is produced so that the amount of copolymer (C) is a desired mass % when the total amount of copolymer (A) obtained in step (1), copolymer (B) obtained in step (1), and copolymer (C) obtained in step (3) is taken as 100 mass %.

[0109] In one embodiment of the step (3), 4-methyl-1-pentene and at least one monomer selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) are added to a slurry containing the copolymer (A) and the copolymer (B), and slurry polymerization of these monomers is carried out.

[0110] In step (3), a slurry containing particles containing copolymer (A), copolymer (B) and copolymer (C) is obtained. The slurry concentration, i.e., the particle concentration, is usually 3 to 50 mass%, preferably 5 to 40 mass%.

[0111] The multi-stage polymerization method can employ slurry polymerization, and the term "slurry polymerization" refers to a polymerization method characterized in that the polymer produced by polymerization is not substantially dissolved in the medium used during polymerization, but exists in the form of, for example, fine particles dispersed in the medium. The multi-stage polymerization is not limited to the slurry polymerization as long as the polymer (X) can be obtained, and can also be carried out by, for example, solution polymerization or gas phase polymerization.

[0112] 《Solid-liquid separation process》 The slurry containing the 4-methyl-1-pentene polymer particles containing the copolymer (A), the copolymer (B) and the copolymer (C) obtained in the step (3) is subjected to solid-liquid separation, for example, filtration, whereby the particles can be separated and recovered.

[0113] Post-processing The 4-methyl-1-pentene polymer particles obtained by the above-mentioned multistage polymerization method, for example, the particles obtained by the above-mentioned solid-liquid separation step, may be subjected to known post-treatment steps such as a catalyst deactivation treatment step, a catalyst residue removal step, a drying step, etc., as necessary, after being produced by the above-mentioned method. In this manner, a mixture of copolymer (A), copolymer (B) and copolymer (C) can be obtained.

[0114] <Additives> The polymer (X) may contain conventionally known additives. Examples of 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, and hydrochloric acid absorbents. The content of the additives is not particularly limited, but is usually 0 to 50 parts by mass, and preferably 0 to 10 parts by mass, for each of 100 parts by mass of the polymer components including the copolymers (A) and (B) and the like. The polymer (X) can contain one or more additives.

[0115] <Method for producing 4-methyl-1-pentene polymer composition (Z)> The 4-methyl-1-pentene polymer composition (Z) of the present invention can be obtained by blending the benzotriazole ultraviolet absorber (Y) at a ratio of 0.05 to 0.5 parts by weight with 100 parts by weight of the 4-methyl-1-pentene polymer (X). In this case, when the 4-methyl-1-pentene polymer composition (Z) is not produced by the multi-stage polymerization described above, the copolymer (A), the copolymer (B) and the copolymer (C) may be used. In addition, other polymer components and additives may be mixed as necessary.

[0116] The components can be mixed by various known methods, for example, by mixing 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 by further melt-kneading the mixture obtained after the above mixing using an apparatus such as a single-screw extruder, a twin-screw extruder, a kneader, or a Banbury mixer, and then granulating or pulverizing the resulting melt-kneaded product.

[0117] <Molded body> The molded article of the present invention can be obtained by molding the above-mentioned 4-methyl-1-pentene polymer composition (Z) by various molding methods. Examples of the molding method that can be used include known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, stamping molding, compressed air molding, vacuum molding, calendar molding, filament molding, foam molding, and powder slush molding. The molded article can be used as an article for various applications, such as food containers, transport containers, medical containers, laboratory equipment, reagent containers, containers for alcoholic drinks such as beer and whiskey, cosmetic containers, and leisure goods. Among these, blown containers are expected to be used in a wide range of applications in terms of economy and molding efficiency. These containers, even if obtained by thermoforming, have excellent ultraviolet ray shielding properties.

[0118] The present invention will now be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0119] Manufacturing Examples 1-3 Preparation of 4-methyl-pentene copolymer (X-1) According to the polymerization method described in Comparative Example 1 (

[0158] ) of WO 2017 / 150265, copolymers (A-1), (B-1), and (C-1) shown in Table 1 were obtained. The polymerization conditions were varied by changing the ratio of 4-methyl-1-pentene, 1-decene, and hydrogen used. The 4-methyl-pentene copolymer (X-1) used in the examples was obtained by mixing the copolymers (A-1), (B-1) and (C-1).

[0120] [Table 1] Structural unit (i): Structural unit derived from 4-methyl-1-pentene Structural unit (ii): Ethylene, a copolymerizable monomer with 4-methyl-1-pentene Or α-olefins with 3 to 20 carbon atoms (However, 4-methyl-1-pentene is excluded.)

[0121] Example 1 <Preparation of 4-methyl-1-pentene polymer composition (Z-1)> A twin-screw extruder (PCM43, manufactured by Ikegai Corporation, screw diameter: 43 mm) was charged with 35 parts by mass of the copolymer (A) obtained in the production example, 45 parts by mass of the copolymer (B), 20 parts by mass of the copolymer (C), and 0.10 parts by mass of Tinuvin 360, a benzotriazole-based ultraviolet absorber (Y). The mixture was then melt-kneaded at 280°C and a rotation speed of 200 rpm using the twin-screw extruder to obtain a polymer composition (Z-1). Preparation of injection test specimens The polymer composition (Z-1) was subjected to injection molding using a 70-ton injection molding machine (M70B) manufactured by Meiki Seisakusho Co., Ltd. under conditions of cylinder temperature: 280°C and mold temperature: 60°C to prepare a square plate-shaped injection test specimen having a thickness of 2 mm.

[0122] Example 2 <Preparation of 4-methyl-1-pentene polymer composition (Z-2)> The same procedure as in Example 1 was carried out, except that the amount of Tinuvin 360, which is the benzotriazole-based ultraviolet absorber (Y), was changed to 0.25 parts by mass. Preparation of injection test specimens A polymer composition (Z-2) was prepared in the same manner as in Example 1.

[0123] Example 3 <Preparation of 4-methyl-1-pentene polymer composition (Z-3)> The same procedure as in Example 1 was carried out, except that the amount of Tinuvin 360, which is the benzotriazole-based ultraviolet absorber (Y), was changed to 0.50 parts by mass. Preparation of injection test specimens A polymer composition (Z-3) was prepared in the same manner as in Example 1.

[0124] Comparative Example 1 <Preparation of 4-methyl-1-pentene polymer composition (Z-4)> The same procedure as in Example 1 was carried out, except that the benzotriazole-based ultraviolet absorber (Y), Tinuvin 360, was not added. Preparation of injection test specimens A polymer composition (Z-4) was prepared in the same manner as in Example 1.

[0125] [Table 2]

[0126] evaluation <Method of measuring physical properties of polymer> The methods for measuring the physical properties of the polymers used in the examples and comparative examples are as follows.

[0127] [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 or an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), which is a copolymerizable monomer with 4-methyl-1-pentene.

[0128] The nuclear magnetic resonance spectrometer used was a JEOL ECP500 type. The solvent was a mixture 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 13 The measurements were performed using C (125 MHz), a sequence of single pulse proton decoupling, a pulse width of 4.7 μs (45° pulse), a repetition time of 5.5 s, and an accumulation count of 10,000 or more, with 27.50 ppm as the reference value for the chemical shift. 13 The amount of structural units derived from 4-methyl-1-pentene and the amount of structural units derived from α-olefins were determined by C-NMR spectroscopy.

[0129] 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 the specific viscosity η was measured in an oil bath at 135° C. sp The decalin solution was diluted with 5 mL of decalin solvent, and the specific viscosity η was measured in the same manner. sp This dilution procedure was repeated two more times, and the η sp The value of / C was calculated as the intrinsic viscosity (see the formula below). [η]=lim(η sp / C) (C→0)

[0130] Melting point (Tm) For each of the polymers used in the examples and comparative examples, the exothermic and endothermic curves were obtained using a 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 carried out as follows. Approximately 5 mg of the sample was placed in a measurement aluminum pan and heated from 20°C to 280°C at a heating rate of 10°C / min. After holding at 280°C for 5 minutes, the temperature was lowered to 20°C at a cooling rate of 10°C / min, and held at 20°C for 5 minutes. The temperature was then raised again from 20°C to 280°C at a heating rate of 10°C / min, and again lowered 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 higher peak temperature was taken as the melting point (Tm).

[0131] Reference example 1, reference example 2, reference example 3 <Measurement of mass loss of benzotriazole-based UV absorber (Y) upon heating> Benzotriazole-based UV absorber (Y) Tinuvin360 (Reference Example 1), Tinuvin 326 (Reference Example 2), Tinuvin 329 (Reference Example 3) The mass loss during heating was measured by the following method. That is, using a thermogravimetric measuring device (TGA-50 model, manufactured by Shimadzu Corporation), 9.9 g of each sample was heated in the range of 20°C to 500°C at 10°C / min under air conditions, and the mass loss due to thermal decomposition of the sample was measured. The temperatures at which the mass of each sample decreased by a specific percentage are shown in Table 3.

[0132] [Table 3]

[0133] <Measuring methods for physical properties of molded bodies> Using a Hitachi High-Tech Science UH4150 ultraviolet-visible-near infrared spectrophotometer, measurements were performed in the range of 200 nm to 850 nm with a sampling interval of 1.0 nm, a scan speed of 300 nm / min, and a slit width of 6.0 nm. Table 2 shows the first wavelength at which the transmittance exceeds 10%, the transmittance at 400 nm, the transmittance at 500 nm, and the transmittance (%) at 600 nm.

[0134] The resin temperature during melt molding of the 4-methyl-1-pentene copolymer (X) used in the present invention is generally around 300° C. On the other hand, as shown in Table 3, Tinuvin 326 and Tinuvin 329 show a clear mass loss at around 300° C., and the ultraviolet absorbing effect is not obtained. In contrast, Tinuvin 360 shows no mass loss up to around 300° C., indicating that it exerts the ultraviolet absorbing effect.

Claims

1. 4-methyl-1-pentene polymer (X) 100 parts by weight, 0.05 to 0.5 parts by weight of a benzotriazole-based ultraviolet absorber (Y), The 4-methyl-1-pentene polymer composition (Z) has a mass loss of 1% or less as determined by TGA analysis (atmospheric conditions, 280° C.) of the benzotriazole ultraviolet absorber (Y).

2. 4-methyl-1-pentene polymer (X) 100 parts by weight, 0.05 to 0.5 parts by weight of a benzotriazole-based ultraviolet absorber (Y), The 4-methyl-1-pentene polymer composition (Z) is characterized in that the benzotriazole ultraviolet absorber (Y) contains two or more benzotriazoles in one molecule.

3. 2. The 4-methyl-1-pentene polymer composition (Z) according to claim 1, wherein the benzotriazole ultraviolet absorber (Y) contains two or more benzotriazoles in one molecule.

4. The 4-methyl-1-pentene polymer composition (Z) according to claim 1 or 2, wherein the benzotriazole ultraviolet absorber (Y) is represented by the following general formula (1): 【Chemistry 1】 In the general formula (1), R １ , R ４ may be the same or different, and each represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, R ５ SO- group or R ５ O ２ - group. R ２ , R ３ may be the same or different, and each represents an alkyl group having 1 to 12 carbon atoms, COO ２ It is an alkyl group having 1 to 12 carbon atoms substituted by an H group, a phenyl group, a phenylalkyl group containing 1 to 4 carbon atoms in the alkyl portion, or a cycloalkyl group having 5 to 8 carbon atoms. R ５ is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group substituted by an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, or the above aryl groups substituted by one or two alkyl groups having 1 to 4 carbon atoms, or a 1,1,2,2-tetrahydroperfluoroalkyl group (the perfluoroalkyl portion of this group consists of 6 to 16 carbon atoms).

5. The 4-methyl-1-pentene polymer composition (Z) according to claim 4, wherein the benzotriazole ultraviolet absorber (Y) is 2,2'-methylene-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol.

6. 4-methyl-1-pentene polymer (X) 15 to 40% by mass of 4-methyl-1-pentene copolymer (A), 40 to 80% by mass of 4-methyl-1-pentene copolymer (B), and 4-methyl-1-pentene copolymer (C) 5 to 30% by mass The 4-methyl-1-pentene polymer composition (Z) according to claim 1 or 2, which consists of the following components and satisfies the following requirements: (The total of copolymer (A), copolymer (B) and copolymer (C) is 100% by mass.) The 4-methyl-1-pentene copolymer (A) satisfies the following requirements (A-i) and (A-ii). Requirements (A-i): The structural unit (i) derived from 4-methyl-1-pentene 97.5 to 100 mol% Ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 2.5 to 0 mol% (However, the total of the structural units (i) and (ii) is 100 mol %). Requirement (A-ii): Intrinsic viscosity [η] Ａ (135°C, decalin) is 1.0 to 5.0 dl / g. The 4-methyl-1-pentene copolymer (B) satisfies the following requirements (Bi) to (B-iii). Requirements (B-i): The structural unit (i) derived from 4-methyl-1-pentene 91.0 to 97.5 mol% Ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 9.0 to 2.5 mol% (However, the total of the structural units (i) and (ii) is 100 mol %). Requirement (B-ii): Intrinsic viscosity [η] Ｂ (135°C, decalin) is 2.0 to 5.0 dl / g. Requirement (B-iii): The melting point (Tm) (measured by DSC) is less than 180°C. The 4-methyl-1-pentene copolymer (C) satisfies the following requirements (C-i) to (C-iii). Requirements (C-i): The structural unit (i) derived from 4-methyl-1-pentene 50 to 91.0 mol% Ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 50 to 9.0 mol% (However, the total of the structural units (i) and (ii) is 100 mol %). Requirement (C-ii): Intrinsic viscosity [η] Ｃ (135°C, decalin) is 2.0 to 5.0 dl / g. Requirement (C-iii): No melting point (Tm) (measured by DSC) is observed.

7. A molded article obtained by molding the 4-methyl-1-pentene polymer composition (Z) according to claim 1 or 2.

8. A blown container obtained by molding the 4-methyl-1-pentene polymer composition (Z) according to claim 1 or 2.

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