Film and manufacturing method thereof

Abstract

To provide a film which contains a 4-methyl-1-pentene-based polymer and has good film thickness accuracy (thickness-thinness accuracy) with little variation in film thickness and heat resistance and further to provide a method for producing a film by inflation molding which has excellent bubble stability, can be stably molded, contains the 4-methyl-1-pentene-based polymer and has thin film thickness and excellent film thickness accuracy.SOLUTION: There is provided a film which contains a 4-methyl-1-pentene polymer composition (X) satisfying the following requirements (X-1) to (X-4). Requirement (X-1): the density is 0.82 to 0.88 g / m3. Requirement (X-2): the melting point (Tm) is 190 to 250°C. Requirement (X-3): the melting enthalpy ΔH is less than 35 J / g. Requirement (X-4): the semi-crystallization time at 215°C measured by DSC is 220 seconds or more or is not measured.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a film containing a 4-methyl-1-pentene polymer and a method for producing the same. [Background technology]

[0002] Compared to polyethylene and polypropylene, 4-methyl-1-pentene polymers are resins with excellent properties such as heat resistance, transparency, light weight, steam resistance, release properties, stain resistance, gas permeability, and electrical properties, and are used in a variety of fields such as food containers, secondary materials for electronic and information components, laboratory equipment, stationery, crosslinking process materials, release films, films for electronic and information components, food packaging materials, and synthetic paper.

[0003] The cast film method is known as a method for producing a film using a 4-methyl-1-pentene polymer, but the cast film method has problems such as only being able to produce a flat film or sheet, and the thickness of the edge portion is likely to be uneven, and the uneven portion (edge ​​portion) must be removed by trimming, resulting in a low yield. For this reason, there has been a demand for a film containing a 4-methyl-1-pentene polymer and having a uniform thickness, and in particular for an inflation film containing a 4-methyl-1-pentene polymer.

[0004] Patent Document 1 describes a method for producing an inflation film using a 4-methyl-1-pentene polymer by extruding a molten resin upward through an inflation die at a temperature 25 to 65°C higher than the melting point and inflating it.

[0005] Patent Document 2 proposes a technology for improving the stretchability of a 4-methyl-1-pentene polymer by using a resin composition containing two types of 4-methyl-1-pentene polymers with different melt flow rates (MFR), and shows that the resin composition can be used for blow molding using a mold. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-62869 [Patent Document 2] Japanese Patent Application Laid-Open No. 2003-292704 Summary of the Invention [Problem to be solved by the invention]

[0007] However, since 4-methyl-1-pentene polymers generally have poor stretchability, even if the production method described in Patent Document 1 is adopted, there is a problem in that the blown film obtained by blown film molding involving stretching is likely to have uneven thickness. Furthermore, even if the resin composition described in Patent Document 2 can be blow molded, the bubble stability is insufficient, and further improvement is required to mold an inflation film with a uniform thickness.

[0008] An object of the present invention is to provide a film that contains a 4-methyl-1-pentene polymer, has little variation in thickness, good thickness precision (thickness / thinness precision), and has heat resistance.Another object of the present invention is to provide a film production method by inflation molding that has excellent bubble stability, allows stable molding, and is capable of producing a film that contains a 4-methyl-1-pentene polymer and has thin thickness precision. [Means for solving the problem]

[0009] In view of the above circumstances, the present inventors have conducted extensive research and found that a film containing a specific 4-methyl-1-pentene polymer composition can solve the above problems, leading to the completion of the present invention. The present invention relates to, for example, the following items [1] to [9].

[0010] [1] A film comprising a 4-methyl-1-pentene polymer composition (X) that satisfies the following requirements (X-1) to (X-4): Requirement (X-1): Density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 . Requirement (X-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190°C to 250°C. Requirement (X-3): Melting enthalpy ΔH is less than 35 J / g. Requirement (X-4): The crystallization half time at 215°C measured by DSC using the following measurement method is 220 seconds or more, or cannot be measured. Method for measuring the crystallization half time: Using a DSC8500 manufactured by PerkinElmer Co., Ltd., the temperature is increased from 30°C to 280°C at a rate of 500°C / min, the temperature is maintained for 10 minutes, and then the temperature is decreased to 215°C at a rate of 500°C / min, and the crystallization half time at 215°C is measured.

[0011] [2] The film according to [1], wherein the 4-methyl-1-pentene polymer composition (X) satisfies the following requirements (X-5) and (X-6): Requirement (X-5): The content of structural units derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of structural units derived from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more than 0 mol% and 10.0 mol% or less. Requirement (X-6): The intrinsic viscosity [η] measured in decalin at 135°C is 1.5 to 8.0 dl / g.

[0012] [3] The film according to [1] or [2], wherein the 4-methyl-1-pentene polymer composition (X) satisfies the following requirement (X-7): Requirement (X-7): The melt tension (MT) measured at 260°C is 25 mN or more.

[0013] [4] The film according to any one of [1] to [3], having an average thickness of 0.1 to 100 μm. [5] The film according to any one of [1] to [4], which is an inflation film. [6] The film according to any one of [1] to [5], which is for packaging.

[0014] [7] A method for producing a film, comprising a step of extruding a 4-methyl-1-pentene polymer composition (X) that satisfies the following requirements (X-1) to (X-4): Requirement (X-1): Density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 . Requirement (X-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190°C to 250°C. Requirement (X-3): Melting enthalpy ΔH is less than 35 J / g. Requirement (X-4): The crystallization half time at 215°C measured by DSC using the following measurement method is 220 seconds or more, or cannot be measured. Method for measuring the crystallization half time: Using a DSC8500 manufactured by PerkinElmer Co., Ltd., the temperature is increased from 30°C to 280°C at a rate of 500°C / min, the temperature is maintained for 10 minutes, and then the temperature is decreased to 215°C at a rate of 500°C / min, and the crystallization half time at 215°C is measured.

[0015] [8] The method for producing a film according to [7], wherein the expansion ratio (bubble ratio) during inflation molding exceeds 1.0. [9] A method for producing a film according to [7] or [8], which comprises producing a film according to any one of [1] to [6]. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a film that contains a 4-methyl-1-pentene polymer, has little variation in thickness, excellent thickness precision (thickness / thinness precision), and has heat resistance. Furthermore, according to the present invention, it is possible to provide a film manufacturing method that can produce a film that contains a 4-methyl-1-pentene polymer, has excellent bubble stability, can be stably molded, and is thin and has excellent thickness precision, and in particular, it is possible to provide a film manufacturing method that uses inflation film molding that involves stretching. DETAILED DESCRIPTION OF THE INVENTION

[0017] The film of the present invention contains a 4-methyl-1-pentene polymer composition (X). <4-methyl-1-pentene polymer composition (X)> The 4-methyl-1-pentene polymer composition (X) according to the present invention contains at least one 4-methyl-1-pentene polymer. In the present invention, the 4-methyl-1-pentene polymer is a polymer or copolymer having structural units derived from 4-methyl-1-pentene, such as a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene with a monomer copolymerizable with 4-methyl-1-pentene. Preferred examples of the copolymer include copolymers of 4-methyl-1-pentene with one or more olefins selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).

[0018] 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. 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, from the viewpoint of obtaining a polymer composition with good moldability. Specifically, 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred. Furthermore, for example, it is preferred to use 1-hexadecene and 1-octadecene in combination.

[0019] In the 4-methyl-1-pentene polymer, the content of structural units derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is not limited to any particular polymer, as long as the amount of structural units in the entire 4-methyl-1-pentene polymer contained in the 4-methyl-1-pentene polymer composition (X) described below falls within a desired range. However, the content is usually 20 mol % or less, preferably 10 mol % or less, more preferably 0.1 to 10 mol %, and even more preferably 0.2 to 8 mol %, relative to 100 mol % of all structural units constituting the 4-methyl-1-pentene polymer. In addition, the content of structural units derived from 4-methyl-1-pentene in 100 mol % of all structural units constituting the 4-methyl-1-pentene polymer is usually 80 mol % or more, and preferably 90 mol % or more.

[0020] The 4-methyl-1-pentene polymer may further contain structural units derived from other polymerizable compounds other than 4-methyl-1-pentene, ethylene, and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), provided that the object of the present invention is not impaired. Examples of other polymerizable compounds 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, and 7-methyl-1,6-octadiene; Examples of non-conjugated polyenes include dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene.

[0021] In the 4-methyl-1-pentene polymer, the content of structural units derived from polymerizable compounds other than 4-methyl-1-pentene, ethylene, and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) 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 copolymer. The 4-methyl-1-pentene polymer can be produced, for example, by a method for producing a 4-methyl-1-pentene polymer described later. Alternatively, commercially available 4-methyl-1-pentene polymers can be used alone or in combination as long as the 4-methyl-1-pentene polymer composition (X) satisfies the properties described later.

[0022] The 4-methyl-1-pentene polymer composition (X) according to the present invention may contain one kind of the above-mentioned 4-methyl-1-pentene polymer alone, or may contain two or more kinds of them in combination.

[0023] Method for producing 4-methyl-1-pentene polymer The 4-methyl-1-pentene polymer constituting the 4-methyl-1-pentene polymer composition (X) can be obtained, for example, by polymerizing 4-methyl-1-pentene, and, if necessary, ethylene and an α-olefin having 3 to 20 carbon atoms, and, if necessary, further, the other polymerizable monomers described above. The 4-methyl-1-pentene polymer constituting the 4-methyl-1-pentene polymer composition (X) of the present invention can be suitably produced by carrying out the polymerization in the presence of a metallocene catalyst.

[0024] Examples of the metallocene catalyst include those described in WO 01 / 53369, WO 01 / 27124, JP 3-193796 A, JP 02-41303 A, WO 06 / 025540 A, and WO 2013 / 099876 A.

[0025] Examples of metallocene catalysts include: a metallocene compound (a); and a support (b).

[0026] <Metallocene compound (a)> The metallocene compound (a) is represented by, for example, general formula (1) or (2).

[0027] [ka]

[0028] The meanings of the symbols in the general formula (1) or (2) are as follows: R 1 ~R 14R are each 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 to each other to form a ring. 5 From R 12 Adjacent substituents up to may be bonded to each other to form a ring.

[0029] 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.

[0030] 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 electron pair. When j is 2 or greater, each Q may be the same or different. j is an integer of 1 to 4, preferably 2.

[0031] R 1 ~R 14 Examples of the hydrocarbon group in include hydrocarbon groups having 1 to 20 carbon atoms, and specific examples 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.

[0032] 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.

[0033] R 1 ~R 14Examples of the silicon-containing group in the formula 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.

[0034] R on the fluorene ring 5 From R 12 Adjacent substituents up to may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, and octamethyloctahydrodibenzofluorenyl.

[0035] 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 11 , R 7 =R 10 , R 8 =R 9 The fluorene ring moiety 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.

[0036] In the case of general formula (1), R 13 and R 14is 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 dialkylmethylene, dicycloalkylmethylene, alkylcycloalkylmethylene, alkylarylmethylene, diarylmethylene, dialkylsilylene, dicycloalkylsilylene, alkylcycloalkylsilylene, alkylarylsilylene, diarylsilylene, and halogenated groups thereof.

[0037] In the case of general formula (2), Y bonds to the divalent hydrocarbon group A to form a cycloalkylidene group, 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.

[0038] 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, and diphenylmethylphosphine, and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane. At least one Q is preferably a halogen atom or an alkyl group having 1 to 20 carbon atoms.

[0039] Specific examples of the metallocene compound (a) include the compounds exemplified in WO 01 / 27124, WO 2006 / 025540, and WO 2007 / 308607.

[0040] The metallocene compound (a) is particularly preferably a compound represented by the following general formula (3), which is described in WO 2014 / 050817 and the like.

[0041] [ka]

[0042] In general formula (3), R 1b is a hydrocarbon group, a silicon-containing group, or a halogen-containing hydrocarbon group, and 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 the respective substituents 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 general formula (1) or (2), and j is an integer of 1 to 4.

[0043] 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.

[0044] R 1b From R 12bExamples of the silicon-containing group in the formula include a group represented by the formula -SiR3 (wherein the multiple Rs are each independently an alkyl group having 1 to 15 carbon atoms or a phenyl group).

[0045] 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 hydrocarbon group are substituted with halogen atoms, such as a trifluoromethyl group. R 2b From R 12b Examples of the halogen atom in the formula include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0046] In general formula (3), examples of the ring (spiro ring, additional ring) formed by bonding two substituents to each other include an alicyclic ring and an aromatic ring. Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, and a cyclopentene ring, and preferred are a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring. Furthermore, such a ring structure may further have a substituent such as an alkyl group on the ring.

[0047] R 1b It is particularly preferred that R is a substituent in which the carbon atom having a free valence (the carbon atom bonded to the cyclopentadienyl ring) is a tertiary carbon atom. 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. 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 is preferably a hydrogen atom from the viewpoint of molecular weight.

[0048] R 2b , R 3b , R 6b and R 7b is preferably a hydrocarbon group having 1 to 20 carbon atoms. 2b and R 3bare bonded to each other to form a ring, and R 6b and R 7b may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include a benzofluorenyl group, a dibenzofluorenyl group, an octahydrodibenzofluorenyl group, a 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group, a 1,1,3,3,6,6,8,8-octamethyl-2,3,6,7,8,10-hexahydro-1H-dicyclopenta[b,h]fluorenyl group, and a 1',1',3',6',8',8'-hexamethyl-1'H,8'H-dicyclopenta[b,h]fluorenyl group.

[0049] R 8b is preferably a hydrogen atom. 9b is preferably an alkyl group having two or more carbon atoms. From the viewpoint of synthesis, R 10b and R 11b is also preferably a hydrogen atom. Alternatively, if n=1, then 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. 11b is preferably a hydrogen atom. R 12b is preferably an alkyl group.

[0050] M is a transition metal of Group 4 of the periodic table, such as Ti, Zr or Hf, preferably Zr or Hf, and particularly preferably Zr.

[0051] n is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. When n is within the above range, it is preferable from the viewpoint of efficiently obtaining the polymer produced. j is an integer of 1 to 4, and is preferably 2.

[0052] As the compound represented by general formula (3), (8-octamethylfluoren-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-tetramethylfluoren)-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 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.

[0053] 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. The carrier (b) contains as a main component an organoaluminum compound (b-1), an organoboron compound (b-2), or an inorganic compound (b-3), or a complex of two or more selected from these.

[0054] Examples of the organoaluminum compound (b-1) include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-normal-octylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, tricycloalkylaluminums, and organoaluminum oxy compounds such as aluminoxanes. Examples of the organoaluminum compound (b-1) include organoaluminum oxy compounds containing boron atoms, halogen-containing aluminoxanes such as those exemplified in WO 2005 / 066191 and WO 2007 / 131010, and ionic aluminoxanes such as those exemplified in WO 2003 / 082879.

[0055] 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.

[0056] Examples of inorganic compounds (b-3) include porous oxides, inorganic halides, clays, clay minerals, and ion-exchange layered compounds. Examples of porous oxides include oxides such as SiO2, Al2O3, MgO, ZrO2, TiO2, BO3, CaO, ZnO, BaO, and ThO2, as well as composites or mixtures containing these. Examples include natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-VO5, SiO2-Cr2O3, and SiO2-TiO2-MgO. Examples of inorganic halides include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halides may be used directly or after pulverization using a ball mill or vibration mill. Alternatively, inorganic halides may be dissolved in a solvent such as alcohol and then precipitated into fine particles using a precipitating agent.

[0057] 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 %, even more preferably 30 to 50 mass %, and particularly preferably 35 to 47 mass %.

[0058] 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.

[0059] The term "solid" means that the solid aluminoxane remains substantially solid in the reaction environment in which it is used. More specifically, this means that the aluminoxane remains solid in the reaction environment in which the components constituting the olefin polymerization catalyst are contacted to prepare a solid olefin polymerization catalyst component, for example, in an inert hydrocarbon medium such as hexane or toluene used in the reaction under specific temperature and pressure conditions.

[0060] The solid aluminoxane preferably contains an aluminoxane having at least one structural unit selected from structural units represented by the following formula (4) and structural units represented by the following formula (5), more preferably contains an aluminoxane having structural units represented by the following formula (4), and even more preferably contains a polymethylaluminoxane consisting solely of structural units represented by the following formula (4):

[0061] [ka]

[0062] [ka]

[0063] In the general formula (4), Me is a methyl group. In general formula (5), 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.

[0064] The structure of solid aluminoxanes is not necessarily clear, but is generally assumed to have a structure in which the structural units represented by formula (4) and / or formula (5) are repeated approximately 2 to 50 times, but is not limited to this structure. The structural units may be bonded in various ways, such as linear, cyclic, or cluster-like, and aluminoxanes are generally assumed to consist of one of these or a mixture of these. Alternatively, aluminoxanes may consist solely of structural units represented by formula (4) or formula (5).

[0065] As the solid aluminoxane, solid polymethylaluminoxane is preferred, and solid polymethylaluminoxane consisting only of the constitutional unit represented by formula (4) is more preferred. The solid aluminoxane functions as a catalyst support, so there is no need to use a solid inorganic support such as silica, alumina, silica-alumina, or magnesium chloride, or a solid organic support such as polystyrene beads, in addition to the solid aluminoxane. Solid aluminoxanes can be prepared, for example, by the methods described in WO 2010 / 055652 and WO 2014 / 123212.

[0066] 《Organic compound component (c)》 The metallocene catalyst may further contain an organic compound component (c) as needed. The organic compound component (c) is used as needed to improve the polymerization performance and the physical properties of the resulting polymer. The organic compound component (c) may be the organoaluminum compound (b-1) described above. Other examples include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0067] <Polymerization Conditions> The polymerization of 4-methyl-1-pentene and, if necessary, ethylene and an α-olefin having 3 to 20 carbon atoms to obtain the 4-methyl-1-pentene copolymer contained in the 4-methyl-1-pentene polymer composition (X) according to the present invention can be carried out by either a liquid-phase polymerization method such as solution polymerization or suspension polymerization, or a gas-phase polymerization method. In liquid-phase polymerization, an inert hydrocarbon solvent can be used. Specific examples 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 these. Alternatively, the olefin containing 4-methyl-1-pentene itself can be used as the polymerization solvent.

[0068] 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. Method (i): Component (a) and component (b) are added to a polymerization reactor in any order. Method (ii): A method in which a catalyst component in which component (a) is supported on component (b) is added to a polymerization reactor.

[0069] In each of the above methods (i) and (ii), component (c) may be further added at any stage, and at least two of the catalyst components may be contacted in advance. In addition, 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.

[0070] When polymerizing a monomer such as 4-methyl-1-pentene using a metallocene catalyst, the amounts of each component that can constitute the metallocene catalyst are as follows: In addition, the content of each component in the metallocene catalyst can be adjusted as follows:

[0071] Component (a) is usually used in an amount of 10 per liter of reaction volume. -10 ~10 -2 moles, preferably 10 -8 ~10 -3 Component (b-1) can be used in an amount such that the molar ratio of aluminum atoms in component (b-1) to the total transition metal atoms (M) in component (a) [Al / M] is usually 10 to 10,000, preferably 30 to 2,000, and particularly preferably 150 to 500. Component (b-2) can be used in an amount such that the molar ratio of component (b-2) to the total transition metal atoms (M) in component (a) [(b-2) / M] is usually 10 to 10,000, preferably 30 to 2,000, and more preferably 150 to 500. Component (b-3) can be used in an amount such that the molar ratio of component (b-3) to the total transition metal atoms (M) in component (a) [(b-3) / M] is usually 10 to 10,000, preferably 30 to 2,000, and more preferably 150 to 500.

[0072] When component (c) is used, if 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; if 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; and if 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.

[0073] The polymerization temperature is usually -50 to 200°C, preferably 0 to 100°C, and more preferably 20 to 100°C. The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, and preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Hydrogen can be added to the polymerization system for the purpose of controlling the molecular weight or polymerization activity of the produced polymer, and the amount of hydrogen added is appropriately about 0.001 to 100 NL per kg of olefin.

[0074] As for the polymerization conditions, it is also possible to adopt multi-stage polymerization in which polymerization is carried out in two or more stages under different reaction conditions. For example, by carrying out stepwise polymerization under two conditions that differ in the amount of hydrogen used or the ratio of 4-methyl-1-pentene to 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.

[0075] The 4-methyl-1-pentene polymer according to the present invention can be produced by polymerizing or copolymerizing 4-methyl-1-pentene and, if necessary, a polymerizable monomer such as an α-olefin in the presence of a polymerization catalyst such as the above-mentioned metallocene catalyst. When the 4-methyl-1-pentene polymer composition (X) according to the present invention is a mixed composition of two kinds of 4-methyl-1-pentene polymers, the first 4-methyl-1-pentene polymer and the second 4-methyl-1-pentene polymer may be produced separately and mixed in a desired mixing ratio. Alternatively, the 4-methyl-1-pentene polymer composition (X) may be produced by a multistage polymerization method including, for example, a step (1) of producing a first 4-methyl-1-pentene polymer by slurry polymerization and a step (2) of producing a second 4-methyl-1-pentene polymer by slurry polymerization in the presence of the polymer obtained in the step (1) such that the amount of the second polymer is a desired % by mass when the total amount of the first and second polymers is 100% by mass.

[0076] The multi-stage polymerization method has steps (1) and (2) which have different polymerization conditions, and may be a two-stage polymerization consisting of steps (1) and (2), or a three-stage or higher polymerization that further includes other steps in addition to steps (1) and (2).

[0077] 《Process (1)》 In step (1), a first 4-methyl-1-pentene polymer 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), which is used as needed, is set so that the amounts of structural units derived from each are in a desired ratio.

[0078] In step (1), a slurry containing the first 4-methyl-1-pentene polymer is obtained. The slurry concentration, i.e., the concentration of the first 4-methyl-1-pentene polymer particles, is usually 0.015 to 45% by mass, and preferably 0.03 to 35% by mass.

[0079] 《Process (2)》 In step (2), a second 4-methyl-1-pentene copolymer is produced by slurry polymerization in the presence of the first 4-methyl-1-pentene polymer 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), which is used as needed, is set so that the amounts of structural units derived from each are in the desired ratio.

[0080] In step (2), the second 4-methyl-1-pentene polymer is produced so that the amount of the second 4-methyl-1-pentene polymer is a desired mass %, assuming that the total amount of the first 4-methyl-1-pentene polymer obtained in step (1) and the second 4-methyl-1-pentene polymer obtained in step (2) is 100 mass %.

[0081] In one embodiment of the step (2), 4-methyl-1-pentene and, if necessary, 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 first 4-methyl-1-pentene polymer, and slurry polymerization of these monomers is carried out.

[0082] In step (2), a slurry containing particles containing the first 4-methyl-1-pentene polymer and the second 4-methyl-1-pentene polymer is obtained. The slurry concentration, i.e., the particle concentration, is usually 3 to 50 mass %, preferably 5 to 40 mass %.

[0083] The multistage polymerization method can employ slurry polymerization, and "slurry polymerization" refers to polymerization 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 multistage polymerization is not limited to slurry polymerization as long as it can produce the 4-methyl-1-pentene polymer composition (X) of the present invention, and can also be carried out by, for example, solution polymerization or gas phase polymerization.

[0084] 《Solid-liquid separation process》 The slurry containing 4-methyl-1-pentene polymer particles containing the first 4-methyl-1-pentene polymer and the second 4-methyl-1-pentene polymer obtained in step (2) is subjected to solid-liquid separation, for example, filtration, to separate and recover the particles.

[0085] Post-processing process The 4-methyl-1-pentene polymer particles obtained by the multistage polymerization method, for example, the particles obtained by the solid-liquid separation step, may be subjected to known post-treatment steps such as a catalyst deactivation step, a catalyst residue removal step, and a drying step, as necessary, after being produced by the method. In this manner, a mixture of the first 4-methyl-1-pentene polymer and the second 4-methyl-1-pentene polymer can be obtained.

[0086] additives The polymer composition (X) of the present invention 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 absorbers. 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 copolymers (A) and (B). The 4-methyl-1-pentene polymer composition (X) of the present invention may contain one or more additives.

[0087] Properties of 4-methyl-1-pentene polymer composition (X) The 4-methyl-1-pentene polymer composition (X) according to the present invention has the same physical properties as conventional 4-methyl-1-pentene polymers, such as excellent heat resistance, transparency, light weight, mold releasability, and stain resistance, and yet has a longer crystallization half time and stretchability than conventional polymer compositions containing 4-methyl-1-pentene polymers. Therefore, a film containing the 4-methyl-1-pentene polymer composition (X) according to the present invention can be made to have a uniform thickness and excellent thickness precision (thickness / thinness precision).

[0088] The 4-methyl-1-pentene polymer composition (X) according to the present invention contains one or more 4-methyl-1-pentene polymers and satisfies the following requirements (X-1) to (X-4): In addition, it is also preferable that the 4-methyl-1-pentene polymer composition (X) further satisfies one or more of the following requirements (X-5) to (X-7).

[0089] Requirement (X-1): Density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 . The density is preferably 0.82 to 0.86 g / m 3 and more preferably 0.82 to 0.84 g / m 3 is. When the density of the 4-methyl-1-pentene polymer composition (X) is within the above range, a lightweight film can be obtained.

[0090] Requirement (X-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190°C to 250°C. The melting point (Tm) is preferably in the range of 190°C to 245°C, more preferably 200°C to 240°C, even more preferably 200°C to 235°C, still more preferably 210°C to 235°C, and particularly preferably 220°C to 235°C. When the melting point (Tm) of the 4-methyl-1-pentene polymer composition (X) is within the above range, heat resistance can be imparted.

[0091] Requirement (X-3): Melting enthalpy ΔH is less than 35 J / g. The fusion enthalpy ΔH is a value measured in accordance with JIS K7122 using the 4-methyl-1-pentene polymer composition (X). The melting enthalpy ΔH is preferably 5 to 30 J / g, and more preferably 8 to 27 J / g. When the melting enthalpy ΔH of the 4-methyl-1-pentene polymer composition (X) is within the above range, the effect of improving the formability into a film can be obtained.

[0092] Requirement (X-4): The crystallization half time (Tc1 / 2) at 215°C measured by DSC using the following measurement method is 220 seconds or more, or is not measurable. Method for measuring the crystallization half time (Tc1 / 2): Using a DSC8500 manufactured by PerkinElmer Co., Ltd., the temperature is increased from 30°C to 280°C at a rate of 500°C / min, the temperature is maintained for 10 minutes, and then the temperature is decreased to 215°C at a rate of 500°C / min, and the crystallization half time at 215°C is measured. Preferably, the crystallization half time is 230 seconds or more or not measured, more preferably 240 seconds or more or not measured, even more preferably 300 seconds or more or not measured, even more preferably 400 seconds or more or not measured, and especially preferably 500 seconds or more or not measured. When the crystallization half time of the 4-methyl-1-pentene polymer composition (X) satisfies the above condition, the crystallization rate during melt molding is slowed, stretchability is improved, and excellent moldability into a film can be obtained.

[0093] Requirement (X-5): The content of structural units derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of structural units derived from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more than 0 mol% and 10.0 mol% or less. The content of structural units derived from 4-methyl-1-pentene is preferably 91.0 to 99.5 mol %, more preferably 92.0 to 99.0 mol %. The content of structural units derived from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is preferably 0.5 to 9.0 mol %, more preferably 1.0 to 8.0 mol %. When the content of the structural units of the 4-methyl-1-pentene polymer composition (X) satisfies the above conditions, the film can be made to have excellent heat resistance, transparency and releasability.

[0094] Requirement (X-6): The intrinsic viscosity [η] measured in decalin at 135° C. is 1.5 to 8.0 dl / g. Specifically, for example, this can be measured by the measurement method described in the examples below. The intrinsic viscosity [η] is preferably 1.6 to 7.0 dL / g, more preferably 1.7 to 6.0 dL / g, even more preferably 1.8 to 5.0 dL / g, still more preferably 1.9 to 4.5 dL / g, and particularly preferably 2.0 to 4.0 dL / g. The 4-methyl-1-pentene polymer composition (X) has an intrinsic viscosity that satisfies the above range, and thus can be formed into a film by a method involving stretching, and is particularly suitable for inflation molding.

[0095] Requirement (X-7): The melt tension (MT) measured at 260°C is 25 mN or more. The melt tension is preferably 26 mN or more, more preferably 26 to 100 mN, and even more preferably 26.5 to 50 mN. The melt tension can be adjusted, for example, by controlling the molecular weight of the polymer. When the 4-methyl-1-pentene polymer composition (X) has a relatively high melt tension that satisfies the above range, it can be formed into a film by a method involving stretching, and is particularly suitable for inflation molding.

[0096] <Film and its manufacturing method> The film of the present invention contains the above-mentioned 4-methyl-1-pentene polymer composition (X). Preferably, the film of the present invention is made of the above-mentioned 4-methyl-1-pentene polymer composition (X) and is obtained by molding the above-mentioned 4-methyl-1-pentene polymer composition (X).

[0097] The film of the present invention is not particularly limited, but the average thickness is usually 0.1 to 1000 μm, preferably 0.1 to 100 μm, more preferably 1.0 to 300 μm, and even more preferably 5 to 200 μm.

[0098] The film of the present invention can be made to have little variation in thickness and excellent thickness precision. Preferably, the film of the present invention has a thickness precision calculated by 2σ÷a×100(%) from the average thickness (a) obtained by measuring at sufficient measurement points and the standard deviation (σ) of the thickness variation, of less than 25, more preferably 23 or less, and even more preferably 20 or less. The average thickness (a) and standard deviation (σ) vary depending on the size of the film, but can be calculated from thickness measurements at 50 equally spaced points, as shown in the Examples described below.

[0099] The film of the present invention may contain the 4-methyl-1-pentene polymer composition (X) described above and can be produced by conventional film-forming methods such as cast molding, extrusion molding, uniaxial stretching, biaxial stretching, and inflation molding. Because the 4-methyl-1-pentene polymer composition (X) has excellent stretchability, it can be preferably produced by inflation molding, which provides excellent bubble stability during inflation molding and allows stable molding. In the case where the film of the present invention is an inflation film produced by inflation molding, it is easy to produce a film with a small thickness, and further, the thickness has little variation and excellent thickness precision, so it is preferred. Furthermore, inflation molding is preferred because it is easy to obtain a film with a uniform thickness throughout, does not require removal of uneven portions, and has excellent production yield. Furthermore, the film of the present invention has excellent releasability because it contains the 4-methyl-1-pentene polymer composition (X).

[0100] Blown Film and Blown Film The film of the present invention is preferably an inflation film obtained by inflation molding. The inflation film according to the present invention can be produced by inflation molding the above-mentioned 4-methyl-1-pentene polymer composition (X).

[0101] The inflation film extrusion can be carried out by a conventionally known inflation film extrusion method capable of forming a film. For example, the inflation film of the present invention can be produced by inflation molding the above-mentioned 4-methyl-1-pentene polymer composition (X) using an inflation film extrusion machine. In the inflation film extrusion, air-cooled inflation film extrusion can be preferably used.

[0102] The conditions for inflation molding are not particularly limited, but the molding temperature is preferably above the melting point of the raw resin used and below 300°C. The expansion ratio (bubble ratio) during inflation molding, which refers to the ratio of the maximum bubble diameter to the die diameter, is preferably greater than 1.0, more preferably 1.1 to 5.0, even more preferably 1.2 to 4.5, even more preferably 1.5 to 4.0, and particularly preferably 1.8 to 3.0. The take-up speed is determined by the film thickness, width, and extrusion rate, and can be adjusted within a range that maintains film formation stability; however, it is generally preferably 1 to 150 m / min, more preferably 1 to 100 m / min.

[0103] The inflation film of the present invention can be suitably used as a material for, for example, packaging materials for daily necessities, food packaging materials, food containers, retort containers, protective films, decorative films / sheets, shrink films, infusion bags, heat-sealing films, medical containers, release films, etc. [Example]

[0104] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples. In the following, the physical properties and the like were measured or evaluated by the following methods.

[0105] <Content of structural units derived from ethylene or α-olefins (excluding 4-methyl-1-pentene)> The content of constitutional units derived from 4-methyl-1-pentene and the content of ethylene or α-olefins (excluding 4-methyl-1-pentene) in the polymer composition (or each polymer) were determined using the following apparatus and conditions: 13 It was calculated from the results measured by C-NMR.

[0106] The ECP500 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. was used. The solvent was a mixed solvent of orthodichlorobenzene / 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 measurement was performed using C (125 MHz), the sequence was single pulse proton decoupling, the pulse width was 4.7 μs (45° pulse), the repetition time was 5.5 s, the number of accumulations was more than 10,000, and 27.50 ppm was used as the reference value for the chemical shift. 13 The content of structural units derived from 4-methyl-1-pentene and the content of structural units derived from ethylene or α-olefins (excluding 4-methyl-1-pentene) were quantified by C-NMR spectroscopy.

[0107] <Intrinsic viscosity [η]> The intrinsic viscosity [η] of the polymer or polymer composition was measured at 135°C using decalin solvent. Approximately 20 mg of polymer powder, pellets, or resin mass was dissolved in 15 mL of decalin, and the specific viscosity ηsp was measured in an oil bath at 135°C. This decalin solution was diluted with 5 mL of decalin solvent, and the specific viscosity ηsp was measured in the same manner. This dilution procedure was repeated two more times, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was used to calculate the intrinsic viscosity (see the formula below). [η]=lim(ηsp / C) (C→0)

[0108] <density> The density was measured in accordance with JIS K7112 (density gradient tube method).

[0109] <Melting point (Tm) and enthalpy of fusion (ΔH)> An exothermic / endothermic curve was obtained using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc. The temperature at the melting peak position during the temperature rise was taken as the melting point (Tm), and the melting peak area at the melting peak was taken as the enthalpy of fusion (ΔH). Calorimetry was performed as follows: Approximately 5 mg of sample was cut out from a 0.5 mm thick injection test piece, placed in an aluminum pan for measurement, 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, then 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 higher peak temperature was taken as the melting point (Tm), and the peak area at the higher melting point was taken as the melting enthalpy (ΔH).

[0110] <Crystallization half time (Tc1 / 2)> The exothermic / endothermic curve was measured using a DSC measuring device (DSC8500) manufactured by PerkinElmer Co., Ltd., and the time when the peak area at 215°C reached half its original value was defined as the half-crystallization time (Tc1 / 2). The measurement was performed as follows: Approximately 5 mg of sample was cut out from a 0.5 mm thick injection test piece, placed in an aluminum pan for measurement, heated from 30°C to 280°C at a heating rate of 500°C / min, held at 280°C for 10 minutes, and then cooled to 215°C at a cooling rate of 500°C / min, and then measured.

[0111] <Melt tension> A Capillograph 1D device manufactured by Toyo Seiki Seisakusho was used. After the sample was placed in a melting furnace (diameter 9.55 mm) set at 260°C and fully melted, it was passed through a capillary with an L / D of 8 / 2.095 mm and an inlet angle of 180° at an extrusion speed of 15 mm / min, and then passed through a pulley fixed 58 cm from the bottom of the capillary. The molten resin was then wound up at a speed of 15 m / min, and the stress applied to the pulley was measured, and this stress was taken as the melt tension.

[0112] <Bubble stability> The bubble stability during inflation molding was evaluated according to the following criteria. ⊚: The bubbles were stable for a long time, and a good film was obtained. ○: Slight movement occurred in the bubble, but stable molding was possible. x: Bubbles fluctuated up and down, causing fluctuations in film width, or molding was not possible.

[0113] <Film thickness, thickness precision> The thickness was measured at 50 points at 1 cm intervals using a thickness measuring dial gauge, and the average value was calculated. The standard deviation (σ) of the measured thickness was doubled (2σ) by the average value, and the resulting value expressed as a percentage (×100) was used as the thickness accuracy. A value of less than 25 was evaluated as ◯, and a value of 25 or more was evaluated as ×.

[0114] <Surface tension> According to JIS K6768, several drops of the wetting reagent mixture were placed on the film, and the test mixture was immediately spread using a cotton swab. If the state of the center of the liquid film remained unchanged after 2 seconds without breaking, it was judged as "wet." If breaking occurred, it was judged as "not wet." The surface tension (mN / m) was recorded when the mixture composition changed from one that did not wet the film to one that was judged to just wet the film. The surface tension is an index of releasability.

[0115] [Polymerization examples A-1 to A-4] In accordance with the polymerization method described in Comparative Example 1 (

[0158] ) of WO 2017 / 150265, the α-olefin was changed to the α-olefin shown in Table 1, and the proportions of 4-methyl-1-pentene, α-olefin, and hydrogen used were changed so that the physical properties of the resulting copolymers would be the values ​​shown in Table 1, thereby obtaining 4-methyl-1-pentene copolymers A-1 to A-4.

[0116] [Polymerization examples A-5, A-6] In accordance with the polymerization method described in Comparative Example 9 of WO 2006 / 054613, the proportions of 4-methyl-1-pentene, other α-olefins (mass mixture of 1-hexadecene, 1-octadecene, etc.), and hydrogen were changed to obtain 4-methyl-1-pentene polymers A-5 and A-6 listed in Table 1.

[0117] [Polymerization examples B-1, B-2] In accordance with the polymerization method described in Production Example 1 (

[0182] to

[0185] ) of JP 2018-162408 A, the α-olefin was changed to the α-olefin shown in Table 1, and the proportions of 4-methyl-1-pentene, α-olefin, and hydrogen used were changed so that the physical properties of the resulting copolymers would be the values ​​shown in Table 1. 4-methyl-1-pentene copolymers B-1 and B-2 were obtained.

[0118] [Table 1]

[0119] [Example 1] Preparation of polymer compositions 70 parts by mass of the polymer A-1 obtained above and 30 parts by mass of polymer B-1 were blended with 0.5 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat stabilizer. The resulting mixture was then granulated using a twin-screw extruder BT-30 (screw diameter 30 mm, L / D = 46) manufactured by Plastics Engineering Research Institute Co., Ltd., at a set temperature of 270°C, a resin extrusion rate of 60 g / min, and 200 rpm to obtain pellets of the polymer composition. The physical properties are shown in Table 2.

[0120] Blown film manufacturing The resulting pellets were used to form a film using a 20 mm diameter inflation molding machine (ring die diameter 30 mm diameter, lip opening 0.7 mm diameter). The molding conditions were adjusted to an extruder temperature of 285°C, a die temperature of 260°C, a take-up speed of 7 m / min, and a bubble diameter of 60 mm diameter relative to the ring die diameter, i.e., an expansion ratio (bubble ratio) of 2.0. The film was blown upward with air cooling, aiming for a film thickness of 20 μm. The bubbles remained stable for a long time, resulting in a good film. The physical properties of the resulting film were evaluated. The results are shown in Table 2.

[0121] [Example 2] Granulation and film formation were carried out in the same manner as in Example 1, except that the 4-methyl-1-pentene polymer used was changed to 32 parts by mass of Polymer A-2 obtained above and 68 parts by mass of Polymer B-2. Although slight fluctuations occurred in the bubbles, stable molding was possible. The physical properties of the obtained film were evaluated. The results are shown in Table 2.

[0122] [Example 3] Granulation and film formation were carried out in the same manner as in Example 1, except that the 4-methyl-1-pentene polymer used was changed to 100 parts by mass of the polymer A-3 obtained above. Bubbles remained stable for a long period of time, and a good film was obtained. The physical properties of the obtained film were evaluated. The results are shown in Table 2.

[0123] [Example 4] Granulation and film formation were carried out in the same manner as in Example 1, except that the 4-methyl-1-pentene polymer used was changed to 100 parts by mass of the polymer A-4 obtained above. Bubbles remained stable for a long period of time, and a good film was obtained. The physical properties of the obtained film were evaluated. The results are shown in Table 2.

[0124] [Comparative Example 1] Granulation and film formation were carried out in the same manner as in Example 1, except that the 4-methyl-1-pentene polymer used was changed to 100 parts by mass of the polymer A-5 obtained above. Bubbles fluctuated up and down, causing fluctuations in film width. The physical properties of the obtained film were evaluated. The results are shown in Table 2.

[0125] Comparative Example 2 Except for changing the 4-methyl-1-pentene polymer used to 100 parts by mass of Polymer A-6 obtained in the above Production Example, granulation and film formation were carried out in the same manner as in Example 1. When attempting to expand the bubble ratio to 2.0, the bubbles began to meander, making it impossible to form a film.

[0126] [Reference example 1] Granulation and film production were carried out in the same manner as in Comparative Example 2, except that the bubbles were not expanded, i.e., the bubble ratio was set to 1.0 and film production was performed without stretching or expanding (air inflation). When the extrusion rate was reduced to aim for a film thickness of 20 μm, the bubbles fluctuated up and down, resulting in fluctuations in film width. When the extrusion rate was adjusted to aim for a film thickness of 40 μm, the bubbles remained stable for a long period of time, and a good film was obtained. The physical properties of the obtained film were evaluated. The results are shown in Table 2.

[0127] [Table 2]

[0128] The results shown in Table 2 above demonstrate that in Examples 1 to 4, which used 4-methyl-1-pentene polymer compositions satisfying all of the requirements (X-1) to (X-4) of the present invention, inflation film molding involving stretching could be stably carried out, and the obtained films had excellent thickness precision.

[0129] On the other hand, in Comparative Example 1, which used a 4-methyl-1-pentene polymer composition that does not satisfy the requirement (X-4) of the present invention, and Comparative Example 2, which used a 4-methyl-1-pentene polymer composition that does not satisfy the requirements (X-3) and (X-4) of the present invention, it was found that the bubbles were unstable and a stable film could not be produced.

[0130] Furthermore, Comparative Example 2 and Reference Example 1 reveal that when a 4-methyl-1-pentene polymer composition is used that does not satisfy the requirements (X-3) and (X-4) of the present invention and has a high melting enthalpy ΔH and a short half-crystallization time, film molding without stretching (film molding at a bubble ratio of 1.0) is possible (see Reference Example 1), but the composition is not suitable for film molding involving stretching and expansion (see Comparative Example 2), and therefore the object of the present invention, which is to provide a film production method by inflation film molding involving stretching, cannot be achieved.

Claims

1. A film comprising a 4-methyl-1-pentene polymer composition (X) that satisfies the following requirements (X-1) to (X-4): Requirement (X-1): Density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 . Requirement (X-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190°C to 250°C. Requirement (X-3): The enthalpy of fusion ΔH is less than 35 J / g. Requirement (X-4): The crystallization half time at 215°C measured by DSC using the following measurement method is 220 seconds or more, or cannot be measured. Method for measuring the crystallization half time: Using a DSC8500 manufactured by PerkinElmer Co., Ltd., the temperature is increased from 30°C to 280°C at a heating rate of 500°C / min, the temperature is maintained for 10 minutes, and then the temperature is decreased to 215°C at a cooling rate of 500°C / min, and the crystallization half time at 215°C is measured.

2. The film according to claim 1, wherein the 4-methyl-1-pentene polymer composition (X) satisfies the following requirements (X-5) and (X-6): Requirement (X-5): The content of structural units derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of structural units derived from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more than 0 mol% and 10.0 mol% or less. Requirement (X-6): The intrinsic viscosity [η] measured in decalin at 135° C. is 1.5 to 8.0 dl / g.

3. The film according to claim 1 or 2, wherein the 4-methyl-1-pentene polymer composition (X) satisfies the following requirement (X-7): Requirement (X-7): The melt tension (MT) measured at 260°C is 25 mN or more.

4. The film according to any one of claims 1 to 3, having an average thickness of 0.1 to 100 µm.

5. The film according to any one of claims 1 to 4, which is an inflation film.

6. The film according to any one of claims 1 to 5, which is for packaging.

7. A method for producing a film, comprising a step of extruding a 4-methyl-1-pentene polymer composition (X) that satisfies the following requirements (X-1) to (X-4): Requirement (X-1): Density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 . Requirement (X-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190°C to 250°C. Requirement (X-3): The enthalpy of fusion ΔH is less than 35 J / g. Requirement (X-4): The crystallization half time at 215°C measured by DSC using the following measurement method is 220 seconds or more, or cannot be measured. Method for measuring the crystallization half time: Using a DSC8500 manufactured by PerkinElmer Co., Ltd., the temperature is increased from 30°C to 280°C at a heating rate of 500°C / min, the temperature is maintained for 10 minutes, and then the temperature is decreased to 215°C at a cooling rate of 500°C / min, and the crystallization half time at 215°C is measured.

8. The method for producing a film according to claim 7 , wherein the expansion ratio (bubble ratio) during inflation molding exceeds 1.

0.

9. The method for producing the film according to claim 7 or 8, which comprises producing the film according to any one of claims 1 to 6.

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