0001]The present invention is 4-methyl-1-pentene polymer having particular physical properties, a resin composition and a molded article comprising the same.
BACKGROUND
[0002]4-methyl-1-pentene as a main constituent monomer 4-methyl-1-pentene · alpha-olefin copolymer, the heat resistance, releasing property, because excellent chemical resistance, widely used in various applications It is. For example, a film made of the copolymer by taking advantage of features such as good mold release, FPC release film is used, such as the composite material forming film and releasing film, or chemical resistance, water resistance, transparency taking advantage of the features such as sex, it has been used such as laboratory instruments and rubber hose manufacturing mandrel.
　On the other hand, the molded article comprising a resin composition containing a conventional 4-methyl-1-pentene polymer, the necessary improvement in view of shape retention, that is, from the viewpoint of heat resistance of when subjected to load at high temperature If there is (e.g., see Patent Document 1). Further, the molded article, the since the low molecular weight component derived from the polymer are present a certain degree, is improved in terms of stain resistance are demanded, used for applications requiring high purity it is also present when it is not possible (for example, see Patent Document 2).
　Patent Document 3, stereoregularity is high, is 4-methyl-1-pentene polymer having a high heat of fusion disclosed in Patent Document 4 utilizing the properties of the polymer, the shape at a high temperature molded retention and stain resistance is improved is disclosed.
CITATION
Patent Document
[0003]
Patent Document 1: JP 2013-122061 Patent Publication
Patent Document 2: JP 2007-224311 Patent Publication
Patent Document 3: International Publication 2014-050817 pamphlet
Patent Document 4: JP 2015-183141 JP
Summary of the Invention
Problems that the Invention is to Solve
[0004]
　As described above, 4-methyl-1-pentene polymer and a molded body according to Patent Documents 3 and 4 has a high stereoregularity and a high heat of fusion, has excellent characteristics in heat resistance. On the other hand, molding in a processing standpoint, especially in large molding apparatus, it is necessary to set much higher than the melting point of the set temperature in order to sufficiently melt the resin, discoloration dirt and the molded article of this molding die , which may cause the molded article surface contamination. According to the study of the present inventors, it can be melted with a small amount of heat, it was found that is also a need for 4-methyl-1-pentene polymer can be molded at a low heat.
[0005]
　A described in Comparative Example of Patent Documents 3 and 4, were polymerized titanium catalyst systems 4-methyl-1-pentene polymer is lower than the polymer according to the examples of Patent Documents 3 and 4 stereoscopic although shows regularity and low heat of fusion, from low molecular weight control, weight low molecular weight component (oligomer) is a number, which discoloration of dirt and molded articles of the molding die, can cause the molded article surface contamination There, it was found that there is a need to improve the stain resistance against this polymer.
[0006]
　Moreover, molded articles obtained from 4-methyl-1-pentene polymer described in Patent Documents 3 and 4 are provided with superior characteristics in heat resistance, etc., according to the study of the present inventors, the film forming neck-in and time, there is room for improvement in drawdown during blow molding, the improvement of formability, the improvement of the melt tension is considered to be effective.
[0007]
　The present invention is an object to solve the above problems of the prior art. That object of the present invention without significant loss of properties such as high heat resistance of the above 4-methyl-1-pentene polymer is to improve the low melting properties and heat of fusion, whereby the vicinity of the melting point to facilitate cold forming at the device temperature, by improving the melt tension of the addition polymer, is improved moldability is to further improve the stain resistance.
Means for Solving the Problems
[0008]
　The present inventors have conducted extensive studies to solve the above problems. As a result, it can solve the above problems by a particular having a composition, and has a specific characteristic 4-methyl-1-pentene polymer, and have completed the present invention.
[0009]
　The present invention relates to the following [1] to [6].
[1] 4-methyl-1-a content of the structural unit derived from pentene 90 to 100 mol%, selected ethylene and 4-methyl-1-pentene other α- olefin of 3 to 20 carbon atoms at least the content of one of the structural units derived from olefins is 0 to 10 mol%, satisfies all the following requirements (a) ~ (f), 4- methyl-1-pentene based polymer (X).
(A) 13 meso diad fraction as measured by C-NMR (m) is in the range of less than 98.0% or more 70.0.
(B) measured by gel permeation chromatography (GPC), the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is in the range between 3.6 and 30. FIG.
(C) conforming to ASTM D1238 and 260 ° C., a melt flow rate measured under the conditions of 5kg load (MFR) is in the range of 0.1 ~ 500 g / 10 min.
Was measured by cross fractionation chromatography apparatus using an infrared spectrophotometer in (d) of detector is the amount of the cumulative weight fraction eluting at 80 ° C. less than 5% by weight.
(E) was measured by gel permeation chromatography (GPC), the molecular weight × 10 1 6 ratio of at least the polymer is not less than 15 mass%.
(F) said measured by differential scanning calorimetry (DSC) 4-methyl-1-pentene polymer heat of fusion and the melting point of the following requirements (i) and satisfying the (ii).
　　　　(I) the following formula (1) is satisfied.
　ΔHm <0.5 × Tm-76 ··· Equation (1)
(In the formula (1), the heat of fusion and ΔHmJ / g, a melting point Tm °
　　　　C..) (Ii) ranges melting point of 180 ~ 260 ° C. It is in.
[0010]
[2] The 4-methyl-1-pentene polymer (X) resin composition comprising according to [1].
[3] [1] molded article comprising a resin composition according to 4-methyl-1-pentene polymer according (X) or the [2].
[4] is an injection molded article or extrusion molded product, the molded body according to [3].
[5] a film, molded article according to [3].
[6] is a blow molded article, molded article according to [3].
The invention's effect
[0011]
　According to the present invention without significant loss of 4-methyl-1-properties such as high heat resistance pentene polymer, excellent melting low heat of fusion, yet high melt tension, further excellent stain resistance , it is possible to provide a 4-methyl-1-pentene polymer and a resin composition.
DESCRIPTION OF THE INVENTION
[0012]
　Hereinafter, according to the present invention 4-methyl-1-pentene polymer (X) (hereinafter simply referred to as polymer (X)), the resin composition containing the polymer (X), and the polymer (X) and it will be described in detail shaped body comprising a resin composition.
[0013]
　<4-methyl-1-pentene polymer (X)>
　4-methyl-1-pentene polymer (X) of the present invention is 4-methyl -1 for all structural units contained in the polymer (X) - a content of the constitutional unit derived from pentene 90 to 100 mol%, of ethylene, and at least one olefin selected from 4-methyl-1-pentene other α- olefin of 3 to 20 carbon atoms (hereinafter , also referred to as a comonomer) 0-10 mol% content of the constitutional unit derived from, satisfying the following requirements (a) ~ (f). Incidentally, the prescribed is 4-methyl-1-pentene polymer (X) is, if a blend of a plurality of 4-methyl-1-pentene polymer, the blend is a requirement (a) ~ means that satisfy (f).
[0014]
　4-methyl-1-pentene polymer (X), for example, 4-methyl-1-pentene homopolymer (i.e., the content of the constitutional unit derived from 4-methyl-1-pentene in 100 mol% there polymers), and 4-methyl-1-pentene and copolymers with other olefins.
[0015]
　Here, from the viewpoint of transparency and heat resistance, in 4-methyl-1-pentene polymer (X), derived from 4-methyl-1-pentene with respect to all the constituent units contained in the polymer (X) configuration the content of units preferably 92 to 100 mol%, more preferably 95-100 mol%, selected from ethylene and carbon atoms 3 ~ 20 alpha-olefin (except 4-methyl-1-pentene) sum of the content of at least one constituent unit derived from olefins, preferably 0-8 mol%, more preferably 0 to 5 mol%.
[0016]
　When 4-methyl-1-pentene polymer (X) is a copolymer, in particular as α- olefin of 4-methyl-1-pentene and the copolymerization to ethylene and 3 to 20 carbon atoms, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Among these are preferably ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, these α- olefins may be singly or in combination of two or more thereof.
[0017]
　In the present invention, 4-methyl-1-pentene polymer (X) in 4-methyl-1-pentene constitutional unit derived from, as well as ethylene and carbon atoms 3 ~ 20 alpha-olefin (4-methyl - of at least one constituent unit derived from olefins selected from 1-excluding pentene) amount is 4-methyl-1-pentene is added during the polymerization reaction, as well as ethylene and carbon atoms 3 ~ 20 alpha- it can be adjusted by the amount of at least one olefin selected from olefins (excluding 4-methyl-1-pentene).
　The following describes each requirement that 4-methyl-1-pentene polymer (X) satisfies.
[0018]
(Requirement (a))
　 13 is in the range meso diad fraction (m) is less than 98.0% or more 70.0 as measured by C-NMR, preferably in the range of less than 98.0% or more 80.0% , more preferably in the range of less than 98.0% or more 90.0%, more preferably in the range of less than 98.0% or more 95.0%.
[0019]
　By 4-methyl-1-meso diad fraction of pentene polymer (X) (m) is not less than the lower limit, the molded body containing 4-methyl-1-pentene polymer (X) is sufficient It becomes one with heat resistance and performance such as rigidity.
　In the present invention, 4-methyl-1-pentene polymer meso diad fraction of (X) (m) can be adjusted by the type of olefin polymerization catalyst described below.
[0020]
(Requirement (b))
　was measured by gel permeation chromatography (GPC), the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is in the range 3.6 to 30, preferably 3. 6-25, and more preferably 3.8 to 25, and further preferably be 4.0 to 25 and especially preferably in the range of 4.0 to 15. Ratio (Mw / Mn) that is in the above range, molded bodies such as films, including 4-methyl-1-pentene polymer (X) is as excellent toughness, internal cracks is the cause of whitening reduced, excellent elongation of the film. Further, the ratio (Mw / Mn) is in the above range, 4-methyl-1-pentene polymer (X) larger polymer having a molecular weight in suggesting that there significant amount. Method of modulating 4-methyl-1-pentene polymer ratio of (X) (Mw / Mn) in the range will be described later in detail.
[0021]
(Requirement
　(c)) 4-methyl-1-pentene polymer (X) is, 260 ° C. in conformity with ASTM D1238, a melt flow rate measured under the conditions of 5kg load (MFR) is 0.1 ~ 500 g / a 10min, preferably 1 ~ 300g / 10min, more preferably 2 ~ 100g / 10min, more preferably 5 ~ 80g / 10min.
[0022]
　When the MFR of 4-methyl-1-pentene polymer (X) is in the above range is preferred in terms of the resin fluidity during molding producing.
　More with the present invention, as the method of adjusting the MFR of 4-methyl-1-pentene polymer (X), to adjust the reactor hydrogen content in the polymerization reaction, a different MFR during or after the polymerization and a method of blending the types of polymers.
[0023]
(Requirement (d))
　was measured by cross fractionation chromatography apparatus using an infrared spectrophotometer detector is the amount of the cumulative weight fraction eluting at 80 ° C. less than 5% by weight.
[0024]
　4-methyl-1-be-pentene polymer (X) the amount of the cumulative weight fraction eluting at 80 ° C. The following is small, the amount of low molecular weight polymer contained in the polymer (X) is less show. The cumulative weight fraction of that in the above range, it becomes possible to suppress the outflow of the low molecular weight component as a contaminant from the molded product obtained from a resin composition containing the polymer, the die during molding molding machines suppressed and contamination, such as, inhibition or discoloration of the molded article obtained, it is possible to effectively perform the suppression of the molded article surface contamination and the content contamination.
　In the present invention, the cumulative weight fraction can be adjusted by the type of olefin polymerization catalyst described below.
[0025]
(Requirement (e))
　was measured by gel permeation chromatography (GPC), the molecular weight of 1 × 10 6 ratio of at least the polymer is not less than 15 wt%, preferably 16 wt% or more, more preferably 17 mass% or more, further preferably 18 mass% or more. The upper limit of the molecular weight is not limited particularly, although depending on the MFR of the polymer (X), is preferably 50 wt% or less, more preferably 40 mass% or less. By the molecular weight is in the above range, 4-methyl-1-pentene polymer (X) has excellent melt tension. The molecular weight × 10 1 6 ratio of the polymer is at least to be in the above range, suggesting that large components of molecular weight is significant amount. 4-methyl-1-pentene polymer molecular weight in the (X) is 1 × 10 6 ratio of at least polymer to coexist hydrogen in the reactor during the polymerization reaction, increasing or decreasing the amount of the hydrogen Accordingly, it is possible to adjust the above range.
[0026]
(Requirement (f))
　satisfies the differential scanning calorimetry 4-methyl-1-pentene polymer as measured by a differential scanning calorimeter (DSC) heat of fusion and the melting point of the following requirements (X) (i) and (ii).
　　　　(I) the following formula (1) is satisfied.
　ΔHm <0.5 × Tm-76 ··· Equation (1)
(In the formula (1), the heat of fusion and ΔHmJ / g, a melting point Tm °
　　　　C..) (Ii) ranges melting point of 180 ~ 260 ° C. It is in.
[0027]
　In the above-mentioned requirement (i), differential scanning calorimetry (DSC) (heating rate: 10 ° C. / min) heat of fusion as measured by (ΔHmJ / g) is preferably 5 ~ 80 J / g, more preferably 10 it is a ~ 60J / g. Further, in the above requirement (ii), differential scanning calorimetry (DSC) (heating rate: 10 ℃ / min) melting point as measured at (Tm ° C.) is preferably 180 ~ 250 ° C., more preferably 200 to 250 ° C., more preferably from 210 ~ 245 ° C..
[0028]
　Above requirements (i) is the heat of fusion for the melting point of such 4-methyl-1-pentene polymer in the present invention (X) indicates that low. That is, by satisfying the requirements (i), while maintaining high heat resistance 4-methyl-1-pentene polymer, that melting is excellent is shown.
　Note that although the present requirement (i), there is disclosed related to the Patent Document 3, there is similarly disclosed in the patent document 4.
[0029]
　In the present invention, heat of fusion of 4-methyl-1-pentene polymer (X) can be adjusted within the above range defined by the use of the olefin polymerization catalyst described below. The melting point can be adjusted by the same time as using the olefin polymerization catalyst, adjusting the proportion of the structural unit of 4-methyl-1-pentene in the requirement (a).
　4-methyl-1-pentene polymer (X) satisfies the above as the requirement (a) ~ (f), satisfy preferably further following requirement (g).
[0030]
(Requirement
　(g)) 260 melt tension at ℃ more than 15 mN, more preferably at least 20 mN. The upper limit is not particularly limited but is usually 100mN less. Melt tension is preferably in moldability and in the above range.
[0031]
<4-methyl-1-producing method of pentene polymer
　(X)> 4-methyl-1-pentene polymer (X) in the presence of an olefin polymerization catalyst described later, 4-methyl-1-pentene copolymerizing at least one olefin selected from by polymerizing, or 4-methyl-1-pentene with ethylene and carbon atoms 3 ~ 20 alpha-olefin (except 4-methyl-1-pentene) it can be obtained by.
[0032]
　 [1-1] olefin polymerization catalyst
　The olefin polymerization catalyst,
the bridged metallocene compound
(A), (B-1) an organometallic compound
(B-2) an organoaluminum oxy-compound
and (B-3) (A) reacting with a compound to form an ion pair
　(referred to hereinafter as "compound (B)" and.) at least one compound selected from a catalyst containing preferably.
[0033]
　
　bridged metallocene compound (A), a compound represented by the general formula [A1] are preferable, the compounds represented by the general formula [A2] are more preferred.
[0034]
[Formula 1]

　In the formula [A1], M is a Group 4 of the periodic table transition metal atom, such as titanium atom, a zirconium atom or a hafnium atom, Q is a halogen atom, a hydrocarbon group, having 10 or less neutral carbon conjugated or nonconjugated diene, the same from anionic ligands, and neutral ligands capable of coordination by lone pair or selected in different combinations, j is an integer of 1 ~ 4, R a and R B may be the same or different from each other, a mononuclear or polynuclear hydrocarbon residue capable of forming a sandwich structure together with M, Y is a carbon atom or a silicon atom, R C and R D are it may be the same or different from each other, a hydrogen atom, a hydrocarbon group, a silicon-containing group, selected from halogen atoms and halogen-containing hydrocarbon group may be bonded to each other to form a ring.
[0035]
[Formula 2]

　wherein [A2], R 1 is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, R 2 ~ R 10 is a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen selected from-containing hydrocarbon group, each may be the same or different, R 2 ~ R 10 may be bonded to each other to thereby form a ring. M is a transition metal of Group 4 atoms of the periodic table, Q is a halogen atom, a hydrocarbon group, conjugated or nonconjugated diene having 10 or less of neutral carbon, it can be coordinated with an anionic ligand, and lone pair from neutral ligand same such, or chosen in different combinations, j is an integer of 1-4.
[0036]
　
　olefin polymerization
catalyst, (B-1) an organometallic compound
(B-2) an organoaluminum oxy-compound
compound to form an ion pair by reacting with (B-3) (A)
selected from at least one compound (B)
preferably contains a.
[0037]
　Specific examples of the compound (B) and later to a carrier (C), the organic compound component (D) is as a disclosed in Patent Documents 3 and 4 or WO 2014-123212. Carrier (C) further on, WO 2010-055652, WO 2011-142400, WO 2013-146337, is applicable example of disclosed in JP 2015-74645.
[0038]
　
　olefin polymerization catalyst is more preferably further comprises a carrier (C).
　The carrier (C), for example, an inorganic or organic compound include granular or particulate solid. Transition metal compound (A) is preferably used in supported form on a carrier (C).
[0039]
　
　　olefin polymerization catalyst of the present invention, further optionally, may also contain (D) an organic compound component. The organic compound component (D) is optionally used for the purpose of improving the physical properties of the polymerization performance and the produced polymer. As the organic compound (D), for example, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers and sulfonic acid salts.
[0040]
　 ratio (Mw / Mn) of 4-methyl-1-pentene polymer (X) is a single-stage or two-stage polymerization multistage polymerization method, a plurality of different molecular weight it can be adjusted by blending of the polymer during polymerization or after polymerization.
[0041]
　Or even single-stage polymerization, it is possible to adjust by dividing the hydrogen by pouring in "polymerization Initial" and "the course of the polymer production" the (Mw / Mn) to any value. More specifically, it polymerizing the high molecular weight polymer, the polymerization is polymerized relatively low molecular weight material by larger amount feed of hydrogen at somewhat advanced stage by a small amount of hydrogen to be introduced into the initial stage of polymerization Accordingly, it is possible to adjust the ratio of the finally obtained polymer (Mw / Mn).
[0042]
<4-methyl-1-pentene polymer resin composition comprising a (X)>
　The resin composition containing a 4-methyl-1-pentene polymer in the present invention (X), the 4-methyl-1 pentene polymer (X) as an essential component, including various components according to the molded body according to the other invention purposes.
[0043]
[4-methyl-1-pentene polymer (X) various components other than]
　4-methyl-1-pentene polymer (X) resin composition comprising, depending on the application, the effect of the present invention other resins or polymers in the inhibition does not range, can optionally contain a resin additive and the like.
[0044]
　Other resins or polymers to be added, can be widely used the following thermoplastic resin (E). The addition amount of these resins or polymers with respect to the total weight of the resin composition is preferably 0.1 to 30 mass%.
[0045]
　Thermoplastic resin (E), according to the present invention 4-methyl-1-pentene polymer (X) and different as long as not particularly limited, for example, the following resins.
　The thermoplastic polyolefin resin, for example, low density, medium density, high density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, polybutene-1, poly-4-methyl-1-pentene, poly 3 - methyl-1-pentene, poly 3-methyl-1-butene, ethylene · alpha-olefin copolymer, propylene · alpha-olefin copolymer, butene · alpha-olefin copolymer, 4-methyl-1 - pentene · alpha-olefin copolymer, cyclic olefin copolymers, chlorinated polyolefins, and modified with a modified polyolefin resin of these olefin resins;
　thermoplastic polyamide resin, for example, aliphatic polyamide (nylon 6, nylon 11 , nylon 12, nylon 66, nylon 610, Na Ron 612),
　a thermoplastic polyester resin; for example, polyethylene terephthalate, polybutylene terephthalate, polyester-based elastomers;
　thermoplastic vinyl aromatic resin, e.g., polystyrene, ABS resin, AS resin, styrene-based elastomers (styrene-butadiene-styrene block polymers, styrene-isoprene-styrene block polymers, styrene-isobutylene-styrene block polymer, a hydrogenated product of the foregoing);
　Thermoplastic polyurethane, vinyl chloride resins, vinylidene chloride resins, acrylic resins, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid acrylate copolymers; ionomers, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, fluorine resin polycarbonate; polyacetals; polyphenylene oxide; polyphenylene sulfide polyimide; polyarylates; polysulfones; polyethersulfones; rosin resin; terpene resins and petroleum resins;
　copolymer rubber, for example, ethylene-alpha-olefin-diene copolymer, propylene-alpha - olefin-diene copolymer, 1-butene, alpha-olefin-diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, Poriisobu Rengomu, natural rubber, silicone rubber and the like.
[0046]
　The polypropylene, isotactic polypropylene and syndiotactic polypropylene. Isotactic polypropylene may be a homopolypropylene, (but excluding propylene) alpha-olefin propylene having 2 to 20 carbon atoms may be a random copolymer may be a propylene block copolymer.
[0047]
　Poly-4-methyl-1-pentene and 4-methyl-1-pentene · alpha-olefin copolymer, the 4-methyl-1-pentene polymer (X) and a different polymer, 4-methyl - homopolymer of 1-pentene, or 4-methyl-1-pentene · alpha-olefin random copolymer. For 4-methyl-1-pentene · alpha-olefin random copolymer, as the 4-methyl-1-pentene and copolymerized alpha-olefins include ethylene, propylene, 1-butene, 1-hexene, 1-octene , 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 2 to 20 carbon atoms, such as, and preferably of 6 ~ 20 alpha-olefins. These may be used singly or in combination of two or more. The melt flow rate (MFR; ASTMD1238, 260 ℃, 5.0kg load) is preferably 0.1 ~ 200 g / 10 min, more preferably 1 ~ 150 g / 10 min. Poly-4-methyl-1-pentene may also be a commercially available product, for example, by Mitsui Chemicals Co., Ltd. TPX (trade name) and the like. In other manufacturers' poly-4-methyl-1-pentene, it can be preferably used satisfy the above requirements.
[0048]
　The polyethylene is manufactured by a conventionally known method, low density polyethylene, medium density polyethylene, high density polyethylene, it can be used high-pressure low-density polyethylene.
[0049]
　The polybutene can be mentioned 1-butene homopolymer and or butene, a copolymer of an olefin other than 1-butene. The olefin to be copolymerized with polybutene, 4-methyl-1-pentene and the mentioned as copolymerized α- olefin α- olefins. These olefins are used alone or in combination of two or more It is. A copolymer, for example, 1-butene-ethylene random copolymer, 1-butene-propylene random copolymer, 1-butene-methylpentene copolymer, 1-butene-methylbutene copolymers, 1-butene- propylene-ethylene copolymer and the like. In such a copolymer, in view of heat resistance, the content of the constitutional unit derived from 1-butene is not less than 50 mol%, more preferably 70 mol% or more, 85% or more there it is particularly preferred.
[0050]
　Modified polyolefin resin, an ethylenically unsaturated bond-containing monomer in the above-mentioned polyolefin resin can be obtained by graft modification with an organic peroxide. The types of functional groups-modified polyolefin having a halogen atom, a carboxyl group, acid anhydride group, an epoxy group, a hydroxyl group, an amino group, amido group, imido group, ester group, alkoxysilane group, an acid halide group and nitrile group such as and the like.
[0051]
　As the rosin-based resin, natural rosin, polymerized rosin, maleic acid, fumaric acid, modified modified rosin, rosin derivatives thereof with (meth) acrylic acid. As the rosin derivative, the natural rosins, polymerized rosins or modified rosins esterified product, phenol modified compounds and their ester and the like. Further, mention may be made also hydrogenated products thereof.
[0052]
　As the terpene resin, alpha-pinene, beta-pinene, limonene, dipentene, terpene phenol, terpene alcohol, include resin composed of terpene aldehydes, alpha-pinene, beta-pinene, limonene, etc. such as styrene dipentene terpene resins aromatic modified obtained by polymerizing aromatic monomers may also be used. Further, mention may be made also hydrogenated products thereof.
[0053]
　The petroleum resin, for example, aliphatic petroleum resins to the C5 fraction Tarunafusa a main raw material, an aromatic petroleum resin and their copolymerized petroleum resin whose main raw material C9 fraction. That, C5-based petroleum resin (resin obtained by polymerizing C5 fraction naphtha cracked oil), C9-based petroleum resin (resin obtained by polymerizing C9 fractions naphtha cracked oil), C5 fraction of C5C9 copolymer petroleum resin (naphtha cracked oil mentioned minute C9 fraction and a copolymerized resin), a styrene such Tarunafusa fraction, indene, coumarone, other coumarone-indene-based resins containing dicyclopentadiene, a p- tertiary butylphenol alkylphenols resin represented by a condensation product of acetylene, o-xylene, p- xylene or m- xylene and xylene-based resins obtained by reacting formalin may also be used.
[0054]
　Further, rosin-based resins, one or more resin selected from the group consisting of terpene resins and petroleum resins, hydrogenated derivatives are preferred because of excellent weather resistance and discoloration resistance. Softening point by ring and ball method of the resin is preferably in the range of 40 ~ 180 ° C.. The number average molecular weight measured by GPC of the resin (Mn) of preferably in the range of about 100 to 10,000. Rosin resin, terpene resin and petroleum resin can be used commercially.
[0055]
　Among these thermoplastic resins (E), preferred are low density, medium density, high density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, polybutene-1, poly-4 methyl-1-pentene, poly 3-methyl-1-pentene, poly 3-methyl-1-butene, ethylene · alpha-olefin copolymer, propylene · alpha-olefin copolymer, butene · alpha-olefin copolymer polymers, styrene elastomer, vinyl acetate copolymer, ethylene-methacrylic acid acrylate copolymers are ionomers, fluorine-based resins, rosin resins, terpene resins and petroleum resins, and more preferred are improving the heat resistance, cold tolerance improvement in terms of flexibility, polyethylene, isotactic polypropylene, Shinji Tactic polypropylene, poly-1-butene, ethylene · alpha-olefin copolymer, propylene · alpha-olefin copolymer, butene · alpha-olefin copolymer, vinyl acetate copolymer, styrene elastomer, a rosin-based resins, terpene resins and petroleum resins.
[0056]
　As the thermoplastic resin (E), preferably poly-3-methyl-1-pentene, poly 3-methyl-1-butene and the like, 4-methyl-1-pentene polymer of the present invention (X by acting as nucleating agents), it contributes to the improvement of rigidity, such as the resulting film.
[0057]
　The thermoplastic resin (E), can either be used alone one from among the thermoplastic resins, it may be used in combination of two or more thereof.
　As the resin additives, for example, nucleating agents, antiblocking agents, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, UV absorbers, antimicrobial agents, surfactants, antistatic agents, weathering stabilizers, heat stabilizers, slip agents, blanking blowing agents, crystallization aids, antifogging, (transparent) nucleating agents, anti-aging agents, hydrochloric acid absorbers, impact modifier, crosslinking agent, co-crosslinking agent, crosslinking aid, adhesive, softening agents, and processing aids. These additives, also alone, can be used in combination or in appropriate combination.
[0058]
　The nucleating agent, 4-methyl-1-formability is further improved pentene polymer (X), i.e. increasing the crystallization temperature, in order to increase the crystallization rate, the use of known nucleating agents possible it is. Specifically, dibenzylidene sorbitol type nucleating agent, a phosphoric acid ester salt-based nucleating agent, a rosin-based nucleating agent, benzoic acid metal salt-based nucleating agent, a fluorinated polyethylene, 2,2-methylenebis (4,6-di -t - butylphenyl) sodium phosphate, pimelic acid or salts thereof, such as 2,6-naphthalenedicarboxylic acid dicarboxylic acid dicyclohexyl amide. The amount of nucleating agent is not particularly limited, 4-methyl-1-pentene polymer (X) with respect to 100 parts by weight, preferably 0.1 to 1 part by weight. Nucleating agent, during polymerization, after polymerization, or may be suitably added at such during molding.
[0059]
　The anti-blocking agent, a known anti-blocking agent can be used. Specifically, fine silica powder, fine powder of aluminum oxide, fine powder clay, powdered or liquid silicon resin, tetrafluoroethylene resin, fine powder crosslinked resins, such as crosslinked acrylic, it is mentioned methacrylic resin powder, etc. it can. Among these, silica fine powder and crosslinked acrylic, methacrylic resin powder are preferred.
[0060]
　As the pigment, inorganic pigments (titanium oxide, iron oxide, chromium oxide, cadmium sulfide), organic pigments (azo lake, thioindigo, phthalocyanine, anthraquinone) and the like. The dye azo, anthraquinone, triphenylmethane and the like. The addition amount of these pigments and dyes are not particularly limited, relative to the total weight of 4-methyl-1-pentene polymer based resin composition, a total of, generally 5 wt% or less, preferably from 0.1 to 3 % by mass.
[0061]
　Glass fibers as the filler, carbon fibers, silica fibers, metal (stainless steel, aluminum, titanium, copper, etc.) fibers, carbon black, silica, glass beads, silicates (calcium silicate, talc, clay, etc.), metal oxides ( iron oxide, titanium oxide, alumina, etc.), carbonates (calcium sulfate of the metal, barium) and various metals (magnesium sulfate, silicon, aluminum, titanium, copper, etc.) powder, mica, glass flake and the like. These fillers may be either singly or in combination of two or more thereof.
[0062]
　Examples of the lubricant, a wax (carnauba wax wax), higher fatty acids (such as stearic acid), higher alcohols (stearyl alcohol, etc.), and higher fatty acid amide (stearic acid amide, etc.).
[0063]
　As the plasticizer, aromatic carboxylic acid esters (dibutyl phthalate), aliphatic carboxylic acid esters (methyl acetyl ricinoleate, etc.), aliphatic Jiarubon ester (adipic acid - propylene glycol type polyester), aliphatic tricarboxylic acid ester (triethyl citrate and the like), phosphoric acid triester (triphenyl phosphate, etc.), epoxy fatty acid ester (epoxy butyl stearate, etc.), petroleum resins.
[0064]
　The release agent, a lower of higher fatty acids (C1 ~ 4) alcohol esters (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4 ~ 30) (hydrogenated castor oil, etc.), glycol esters of fatty acids, such as liquid paraffin and the like.
[0065]
　As the antioxidant, a known antioxidant can be used. Specifically, phenol (2,6-di -t- butyl-4-methylphenol), polycyclic phenol (2,2'-methylenebis (4-methyl -6-t-butylphenol), phosphorus system (tetrakis (2,4-di -t- butyl-phenyl) -4,4-biphenylene phosphonate, etc.), sulfur-based (dilauryl thiodipropionate and the like), amine (N, N-diisopropyl -p- phenylenediamine), antioxidant of lactone and the like, in combination several of these may be used.
[0066]
　As the flame retardants, organic flame retardant (nitrogen-containing, sulfur-containing, silicon-Motokei, phosphorous-based, etc.), an inorganic flame retardant (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.) and the like.
[0067]
　As the ultraviolet absorber, benzotriazole-based, benzophenone-based, salicylic acid-based, acrylate-based, and the like.
　Antibacterial agents, quaternary ammonium salts, pyridine based compounds, organic acids, organic acid esters, halogenated phenol, and organic iodine.
[0068]
　As the surfactant can be exemplified nonionic, anionic, surfactants cationic or amphoteric. Nonionic surfactants, higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol polyethylene glycol type nonionic surfactants of ethylene oxide adducts, polyethylene oxide, fatty esters of glycerol , fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and polyhydric alcohol type nonionic surfactants such as fatty amides of alkanolamines. Examples of the anionic surfactant, for example, sulfuric acid ester salts such as alkali metal salts of higher fatty acids, alkyl benzene sulfonates, alkyl sulfonates, sulfonate salts such as paraffin sulfonates, such as higher alcohol phosphoric acid ester salt and phosphoric acid ester salts. Examples of the cationic surfactant, such as quaternary ammonium salts such as alkyl trimethyl ammonium salts. Examples of the amphoteric surfactant, higher alkyl amino acid salts amino acid type amphoteric surfactants such as higher alkyl dimethyl betaines, such as betaine type amphoteric surfactants such as higher alkyl time hydroxyethyl betaine.
[0069]
　As the antistatic agent, said surfactant, fatty acid esters, polymeric antistatic agent. As the fatty acid ester include stearic acids and esters of oleic acid, polyether ester amides as polymer type antistatic agent.
[0070]
　The filler, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, UV absorbers, antimicrobial agents, surfactants, amount of various additives such as antistatic agents, to impair the object of the present invention depending on the application with no range is not particularly limited, relative to the total weight of the resin composition containing 4-methyl-1-pentene polymer (X), respectively, is 0.1 to 30 mass% it is preferable.
<4-methyl-1-pentene polymer (X) method for producing a resin composition containing>
　manufacturing method according to the present invention 4-methyl-1-pentene polymer (X) resin comprising the composition especially but are not limited to, for example, were mixed 4-methyl-1-pentene polymer (X) and the other ingredients in the proportion of the added above, obtained by melt-kneading.
[0071]
　The method of melt kneading is not particularly limited, it is generally possible to perform using a melt kneading apparatus such as an extruder which is commercially available.
　For example, a cylinder temperature of a portion performing kneading in the kneading machine is usually 220 ~ 320 ° C., preferably 250 ~ 300 ° C.. Kneading is insufficient due to the low and insufficient melting of the cylinder temperature of 220 ° C., the improvement of the physical properties of the resin composition is hard to see. On the other hand, if the temperature is higher than 320 ° C., there are cases where thermal decomposition of the 4-methyl-1-pentene polymer (X) takes place. The kneading time is usually 0.1 to 30 minutes, particularly preferably 0.5 to 5 minutes. Kneading time is not performed sufficiently kneading the less than 0.1 minutes, also, there is a case where the kneading time occurs thermal decomposition of more than 30 minutes when 4-methyl-1-pentene polymer (X) .
[0072]

　molded body obtained by molding the resin composition.
(1) Molding method
　The molding method of the resin composition can be applied various known molding methods such as injection molding or extrusion molding, injection stretch blow molding method, a blow molding method, cast Bok molding, calendering one molding law, press molding, stamping molding, inflation molding, may be mentioned various molding methods roll forming or the like. These molding methods, molded article of interest, such as films, sheets, hollow moldings, injection moldings, can be processed into fibers. Molding conditions are the same as molding conditions known 4-methyl-1-pentene polymer.
[0073]
(2) Shape
　There is no particular restriction on the shape of the molded body. For example, tubular, film, sheet, film (membrane) shape, a tape shape, a plate shape, rod-like, fibrous, nonwoven fabric, or the like.
　In the following, the film is a general term for planar moldings, sheets, and concept including a tape.
[0074]
(3) Use
　the molded body of the present invention may be used without limitation to conventional 4-methyl-1-pentene polymer can be used application.
　Elongation of the film is required as characteristics at the time of film, there is no limitation on the application of the film. The use of the film, for example, food, meat, processed fish, vegetables, fruits, fermented food, retort food, confectionery, pharmaceutical, bulbs, seeds, and the packaging material of mushrooms, etc., wrap film, cell culture back, cell inspection film heat vacuum molded container, daily dishes containers, delicatessen lid material, baking cartons, various release film.
[0075]
　The Applications of the molded body according to the present invention set forth below, but not particularly limited to.
　The container, for example, tableware, tone昧料container, kitchenware, retort container, frozen storage container, retort pouches, microwave oven heat-resistant container, frozen food containers, frozen dessert cups, cups, baby bottles, food containers such as beverage bottles, or such as a bottle container, blood transfusion sets, medical bottles, medical containers, medical hollow bottle, medical bag, infusion bag, blood storage back, infusion bottle, chemical container, detergent container, for a flexible container, bleach containers, shampoo containers, rinse containers, cosmetic containers, perfume container, Bok toner container, the powder container, the container adhesives, containers for gasoline tanks, kerosene containers, food containers, heat-resistant containers, medical containers, animal cages, physicochemical experimental equipment, and the like.
[0076]
　As a packaging material, for example, food packaging materials, meat packaging material, processed fish packaging materials, vegetable packaging materials, fruit packaging material, fermented food packaging materials, confectionery packaging material, the oxygen absorbent packaging material, retort food packaging materials, freshness holding the film, pharmaceutical packaging material, a cell culture bag, cystoscopy film, bulbs, packaging materials, seed dressing, vegetables, mushroom film, heat vacuum molded container, daily dishes containers, delicatessen lid material, commercial wrap films, household use wrap film, such as baking cartons and the like.
[0077]
　The film other than the above, for example, release film for a flexible printed board, release films for ACM substrate, a release film for a rigid substrate, a release film for a rigid flexible substrate, a release film for advanced composite materials, carbon fiber composite release film for wood curing, glass fiber composite release film for curing, aramid fiber composite curing release film, release film for curing the nanocomposite, release film for curing filler filling material, disconnecting semiconductor encapsulation mold film, release film for a polarizing plate, a release film for a diffusion sheet, a release film for a prism sheet, a release film reflection sheet, cushion film for release film, release film for a fuel cell, disconnecting various rubber sheets mold film, release film for urethane curing, release film such as release film for epoxy curing, solar cells Le sealing sheet, a solar cell backsheet, plastic film for solar cell, a battery separator, the separator for lithium ion batteries, fuel cell electrolyte membrane, an adhesive-adhesive separator, the light guide plate, an optical disk, a dicing tape back-grinding tape die bonding film, two-layer FCCL, substrate-adhesive separator for a semiconductor process films such as films capacitor films, adhesive films, stress relaxation film, pellicle film, film for a polarizing plate, protective film for a polarizing plate, a liquid protective film for goods panel, a protective film for optical parts, protective film for lens, protective film for electrical parts and appliances, the protective film for mobile phones, protective film for PC, protective film for a touch panel, window glass protection film, for baking finish Irumu, masking film, capacitor film, the capacitor film, the tab lead film, a fuel cell capacitor film, reflective film, diffusion film, (including glass) laminates, the protective film of the radiation-resistant film, resistance to γ ​​ray films, such as porous film , heat dissipation film sheet, the sealed electronic component manufacturing mold, LED mold, laminate for high-frequency circuits, high-frequency cable covering material, the optical waveguide substrate, glass fiber
[0078]
　Other applications, for example, rubber hose manufacture mandrel, sheath, rubber hose manufacture sheath, hose, tube, if skin for release paper, medical tubing, industrial tubes, cooling water piping, hot water piping, electric wire covering material, a millimeter wave signal cable covering material, the high-frequency signal cable covering material, Eco wire covering material, automotive cable covering material, the signal cable coatings, insulators for high-voltage wire, cable duct, cosmetics and perfumes spray tubes, medical tubing, infusion tube, Paifu, wire harness, two-wheeled automobiles, auto, railway vehicle, aircraft, interior and exterior material such as a ship, abrasion-resistant automotive interior and exterior material, instrument panel skin, door trim, rear package trim skin, ceiling skin, rear pillar skin, sheet back garnish, console box, armrest, an air bag case Li De, shift knob, assist grips, side step mat, the meter cover, battery cap, fuse, automatic washing sensor parts, ignition, coil bobbins, bushings, bumpers, car heater fan, radiator grille, wheel cap, power supply connector for EV, automotive displays polarizing plates, louvers, armrests, rail insulation version, motorcycle windproof, reclining cover, trunk in the seat, the seat belt buckle, inner-outer mall, bumper molding, side molding, roof molding, molding material, such as a belt molding, air spoiler, door seals , automotive sealing material such as a body seal, glass run channel, mudguards, kicking plate, step mat, number plate housing, automotive hose member, air Kutohosu, air duct cover, the air intake pipe, air dam skirt, timing belt cover seal, hood cushion, door cushion, cup holders, side brake grip, shift knob cover, seat adjustment knob, wire harness grommet, suspension cover boots, glass guide, inner belt line seals, roof guides, trunk lid seals, molded quarter window Gasquet Tsu door, corner moldings, glass encapsulation Shiyu configuration, hood seal, glass run channels, secondary seal, bumper parts, body panels, side shields, door skin, weather strip material, hoses, steering wheel, wire harness cover, seat adjusters cover, such as automotive interior and exterior materials, damping tire, static and dynamic stresses tires, car race tires, special tires, such as radio-controlled tire, packing, automotive dust cover, lamp seal, automotive boots material, rack-and-pinion boots, timing belt, wire harness, grommet, emblems, air filter packing, connectors for automobiles evening, ignition coil, switch, lamp reflector, relay, electric control unit case, sensor housing, the head Lamp, meter panel, insulator, bearing retainer, thrust washers, lamp reflector, door handles, glazing, panorama roof, Sorenoibarubu, ECU case, connector unit connection, an alternator, terminal blocks HEV, solenoid valves, coils sealing parts, furniture and footwear, apparel, bags, skin material such as building materials, building sealing material, waterproof sheet, building materials sheet, pipe fittings, vanity, bathroom ceiling, the impeller, building materials gasket, building materials for window film, iron core protection member, soil improvement use sheet, water stop material, joint material, gasket, door, door frame, window frame, Mawarien, baseboards, opening frame or the like, flooring, ceiling material, wallpaper, health supplies (for example, non-slip mat sheets, fall safety film mat sheet), health equipment member, shock absorbing pads, the protector protection (eg helmet , Guard), sporting goods (for example: Sports grip, protector), sports armor, racket, mouth guard, ball, golf ball, transport equipment (for example: Carrying shock absorbing Guriffu, impact-absorbing sheet), the damping pallet, shock-absorbing damper, insulator, for footwear shock absorber, shock absorbing foams, shock absorbing film and sheet impact absorbing material such as a grip material (writing instrument, tool, sports equipment, Steering wheel, daily necessities, electrical appliances, furniture, etc.), the camera body and parts, OA equipment parts, copier structural parts, printer structure parts, aircraft members, flight meal trays, facsimile structural parts, pump parts, electric tool parts, drying washing machine parts, heater pump ejection port, outlet, IH rice cooker, rice cooker in the lid, range roller Stay ring, vacuum cleaner fan guide, the pump filter case for electronic jar, garbage processing machine parts and processing tank-heating and drying parts, milk for the meter, filter bowl, escalator parts, ultrasonic motor Howe Packaging, absolute encoder, a small pump housing, TV member, hair dryer housing, lighting cover, miscellaneous goods, coffee dripper, humidifier parts, iron parts, water supply equipment parts, water bottle, comb, fountain pen, pencil, pencil sharpener, sports leisure goods, skiing goggles, karate, kendo armor, surfing fins, musical instruments, fish tank, sandals, shoveling snow shovel, fishing rod case, toys, shoe soles, the bottom sole, shoe midsole, inner sole, sole, sandals, chairs the epidermis, bag, school bags, hardware, such as jumper Court, strip, rod, ribbon, notebook covers, book covers, key chains, pencil case, wallet, chopsticks, astragalus, microwave cooking pot, put a business card, put regular, sucker, toothbrush, flooring, gymnastics mat, electric tool member, farm equipment member, heat dissipating material, transparent Plate, soundproofing materials, sound absorbing material, a cushioning material, wire cable, shape memory materials, connectors, switches, plugs, appliance parts (motor parts, housings, etc.), medical gaskets, speaker diaphragm, medical cap, Kusurisen, gasket after filling the baby food, dairy products, pharmaceuticals, sterile water or the like into the bottle, boiling treatment, packing material applications are such high temperature treatment pressure steam sterilization, industrial sealing materials, industrial sewing table, number plate housing, Pettobo Cap liner, such as torque cap liner, protective film adhesive layer, an adhesive material such as a hot melt adhesive material, stationery, office supplies, OA Purintaashi, FAX leg, sewing machine leg, motor support mat, precision equipment such as audio vibration-proof material, OA equipment support member, OA heat resistant packing, animal cages, beaker, physics and chemistry laboratory equipment, such as a graduated cylinder, medical film sheets, films and sheets for cell culture, syringes, CD / DVD / Blu-ray such as optical media, for optical measurement cells, wardrobe, clear case clear file, clear sheet, desk mats, as use as fibers, for example, monofilament, multifilament, cut fibers, hollow fibers, non-woven, the stretchable nonwoven fabric, fibers, tarpaulins, breathable textiles and cloth, disposable diapers, sanitary napkins, hygiene , Filter, bag filter, dust collection filter, air cleaner, the hollow fiber filter, water filters, taking into cloth, Omonbakakami, gas separation membranes, artificial liver (Case, hollow fiber), filter machine reverse osmosis membrane, the heart-lung machine, the syringe syringe, stopcock, infusion set, the surgeon instrument, flow meters, dental instruments, contact lenses disinfecting instruments, inhalation mask, analytical cell, milking machines, fire alarms, extinguishers, helmets, safety glasses, IC carrier, pickup lens, the burn-in socket, and the like.
[0079]
　Moreover, coating materials, films obtained by coating a sheet, release material, Tomizuzai, insulating film, adhesive material, adhesive material, coated paper, transparent sealants, sealants, hot melt adhesive, solvent type adhesive agents, film-like adhesive, cloth tape, kraft tape, is suitably used for the like elastic adhesive.
[0080]
　Also, the 4-methyl-1-pentene polymer (X) can also be processed into a fine powder by grinding process. The resulting fine powder was as additives for example ink compositions or coating compositions, as additives metallurgical powder composition, as additives of the ceramic sintered powder composition, as additives for adhesives, rubber as additives, as a release agent in the toner it can be used as such as mold release agents. Further, fine powder obtained, the shaft, gears, cams, electrical parts, camera parts, automobile parts, as a resin additive to components for household products, waxes, greases, engine oils, fine ceramics, plated It can also be used as a resin additive such as.
Example
[0081]
　Next will be described on the basis of the present invention in detail referring to Examples, but the present invention is not limited to these examples.
Synthesis -1 of a transition metal complex]
　by the method described in WO 2001/027124, dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di -tert- butyl - was synthesized fluorenyl) zirconium dichloride. The compounds are described as "catalyst (A)".
[0082]
　A magnetic stirrer is put into a Schlenk tube purged with nitrogen sufficiently dried, it was placed in the catalyst (A) 30.7 mmol as the bridged metallocene compound. It was added at room temperature with stirring catalyst (A) a 500 equivalent of aluminum atom in terms relative to modified methylaluminoxane suspension (n- hexane solvent), the amount of catalyst (A) is 5.0 mmol / mL added decane to prepare a catalyst solution (slurry (a-1)) a.
[0083]
　The slurry prepared above (A-1), under a nitrogen stream, decane solution of diisobutylaluminum hydride to (2.0 mmol / mL of aluminum atoms terms) 2.0 mL, a further 3-methyl-1-pentene 7. 5mL (5.0g) was charged. Stirring was stopped after 1.5 hours, the resulting prepolymerized catalyst component was washed 3 times with decane 50mL by decantation. The prepolymerized catalyst component was suspended in decane, decane slurry (A-2) 50mL.
[0084]
Synthesis -2 transition metal complex]
　by the method described in WO 2005/121192, diphenylmethylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (2,7-di -tert- butyl - was synthesized fluorenyl) zirconium dichloride. This compound also referred to as "catalyst (B)".
[0085]
　A magnetic stirrer is put into a Schlenk tube purged with nitrogen sufficiently dried, it was placed in the catalyst (B) 32.8 mmol as the bridged metallocene compound. Was added at room temperature with a catalyst (B) becomes 500 equivalents of aluminum atoms in terms relative to modified methylaluminoxane suspension (n- hexane solvent) was stirred, an amount of the catalyst (B) is 2.5 mmol / mL added decane to prepare a catalyst solution (slurry (B-1)) a.
[0086]
　The slurry prepared above (B-1), under a nitrogen stream, decane solution of diisobutylaluminum hydride to (2.0 mmol / mL of aluminum atoms terms) 2.0 mL, a further 3-methyl-1-pentene 7. 5mL (5.0g) was charged. Stirring was stopped after 1.5 hours, the resulting prepolymerized catalyst component was washed 3 times with decane 50mL by decantation. The prepolymerized catalyst component was suspended in decane, decane slurry (B-2) 50mL.
[0087]
Synthesis -3 transition metal complex]
　by the method described in WO 2001/027124, dimethyl - was synthesized [3-tert-butyl-5-methylcyclopentadienyl] (fluorenyl) zirconium dichloride. The compounds are described as "the catalyst (C)".
[0088]
　A magnetic stirrer is put into a Schlenk tube purged with nitrogen sufficiently dried, it was placed in the catalyst (C) 32.8 mmol as the bridged metallocene compound. It was added at room temperature with stirring catalyst (C) a 500 equivalent of aluminum atom in terms relative to modified methylaluminoxane suspension (n- hexane solvent), the amount of catalyst (C) is 2.5 mmol / mL added decane to prepare a catalyst solution (slurry (C-1)).
[0089]
　The slurry prepared above (C-1), under a nitrogen stream, decane solution of diisobutylaluminum hydride to (2.0 mmol / mL of aluminum atoms terms) 2.0 mL, a further 3-methyl-1-pentene 7. 5mL (5.0g) was charged. Stirring was stopped after 1.5 hours, the resulting prepolymerized catalyst component was washed 3 times with decane 50mL by decantation. The prepolymerized catalyst component was suspended in decane, decane slurry (C-2) 50mL.
[0090]
[Synthesis of transition metal complex
　-4] (8-octamethyl fluorene-12'-yl - (2- (adamantan-1-yl) -8-methyl -3,3b, 4,5,6,7,7a, 8 octahydrocyclopenta [a] indene)) zirconium dichloride (synthesis of catalyst D)
　(1) 1-synthesis of adamantyl cyclopentadienyl lithium
　under a nitrogen atmosphere, ethyl magnesium bromide 1.0M concentration 200ml three-necked flask It was charged with tert- butyl methyl ether solution 40 ml. This solution was added dropwise over a cyclopentadiene 2.64 g 20 minutes while cooling in an ice bath, and stirred for 17 hours cooled to room temperature, the solution D-1 was prepared.
[0091]
　Under a nitrogen atmosphere, it was charged to a 500ml three-necked flask diisopropyl ether 200 ml, trifluoromethanesulfonate, copper and (II) 0.36 g. Under a water bath, to this solution was added dropwise over a solution D-1 of the previously prepared 20 minutes. Bromo adamantane 4.30g was added dropwise a solution prepared by dissolving diisopropyl ether 40 mL, and stirred for 10 hours at 70 ° C.. The reaction solution was cooled to room temperature, water bath under addition of saturated aqueous ammonium chloride solution 200 ml. The organic layer was separated, subjected to extraction with hexane 200ml to water layer, the hexane after extraction was previous organic layer and combined resultant organic solution was washed with water. After the organic solution was dried over magnesium sulfate, the solvent was distilled off. The resulting solid by purifying by silica gel column chromatography to obtain a crude product of 4.2 g.
[0092]
　Under a nitrogen atmosphere, to a 100ml Schlenk flask and the resulting crude product 4.2 g, was charged with hexane 20 mL. Ice bath, a hexane solution 13.8mL of n- butyl lithium 1.6M in this solution was added dropwise over 20 minutes and stirred for 17 hours to return to room temperature. It was filtered and the precipitate from the reaction mixture, by washing with hexane to obtain the target product 1-adamantyl-cyclopentadienyl lithium. Yield 2.70 g, it was 66% yield.
　 1 the result of the measurement of the H-NMR, was identified the desired product. Measurement results are as follows.
　 1 H-NMR (THF-d 8 ): Deruta5.57-5.55 (2H, m), 5.52-5.50 (2H, m), 1.96 (3H, s), 1.87 ( 6H, s), 1.74 (6H , s).
[0093]
　(2) 2- (adamantan-1-yl) -8-methyl -3,3b, 4,5,6,7,7a, 8- octahydrocyclopenta [a] Synthesis of indene
　nitrogen atmosphere, 100 ml three-necked flask He was charged THF40ml, the magnesium chloride 1.57g to. To this solution was added dropwise over a solution obtained by dissolving 1-adamantyl-cyclopentadienyl lithium 3.09g in 10 ml of THF 5 minutes and stirred for 3 hours at 2 hours, further 50 ° C. at room temperature. Ice / acetone bath under a solution obtained by dissolving 1-acetyl-cyclohexene 1.96g of (15.75 mmol) in THF10ml was added dropwise over 10 minutes, followed by stirring at room temperature for 19 hours. Ice / acetone bath under acid 1.0 ml, was charged with pyrrolidine 3.1 ml, and stirred at room temperature for 17 hours. Ice / acetone bath under addition of saturated aqueous ammonium chloride solution 30ml to the solution. This solution was added with hexane 100ml, the organic layer was separated, subjected to extraction with hexane 200ml to water layer, twice with hexane after extraction previous organic layer and combined resultant organic solution with water wash did. After the organic solution was dried over magnesium sulfate, the solvent was distilled off. Recrystallization of the resulting solid from methanol, the desired product 2- (adamantan-1-yl) -8-methyl -3,3b, 4,5,6,7,7a, 8- octahydro cyclopenta [a] indene. Yield 2.134g, it was 47% yield.
　 1 H-NMR, the measurement results of GC-MS, was identified the desired product. Measurement results are as follows.
　 1 H-NMR (BY TOLUENE-d 8 ): Deruta6.06 (IH, s), 5.98 (IH, s), 2.88-2.78 (2H, m), 1.98-1.13 ( 26H, m).
　GC-MS: m / z = 306 (M + ).
[0094]
　(3) 8-octamethyl fluorene-12'-yl - (2- (adamantan-1-yl) -8-methyl -3,3b, 4,5,6,7,7a, 8- octahydrocyclopenta [ a] indene) synthesis of
　nitrogen atmosphere, was charged octamethyl fluorene 1.546G, a tert- butyl methyl ether 40ml to 30ml Schlenk tube. Ice / acetone bath was added dropwise under over hexane solution 2.62ml of n- butyl lithium 1.6M in this solution for 15 minutes. Gradually and the mixture was stirred for 22 hours while returning to room temperature. The solution of 2- (adamantan-1-yl) -8-methyl -3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene 1.349g was added. 19 hours at room temperature, was further stirred for 8 hours at 50 ° C., it was added to the reaction solution, a saturated aqueous solution of ammonium chloride 100 ml. The organic layer was separated, subjected to extraction with hexane 100ml to water layer, the hexane after extraction was previous organic layer and combined resultant organic solution was washed twice with water. After the organic solution was dried over magnesium sulfate, the solvent was distilled off. The resulting solid was the washed with acetone, the desired product 8-octamethyl fluorene-12'-yl - (2- (adamantan-1-yl) -8-methyl -3,3B, 4, 5, 6,7,7A, to give 8-octahydrocyclopenta [a] indene). Yield 1.51 g, it was 54% yield.
[0095]
　The measurement results of FD-MS, was identified the desired product. Measurement results are as follows.
　MS-FD: M / Z = 693 (M Tasu ).
　 1 from H-NMR measurement results of the resulting 8-octamethyl fluorene-12'-yl - (2- (adamantan-1-yl) -8-methyl -3,3B, 4, 5, 6, 7, 7a, 8- octahydrocyclopenta [a] indene) was confirmed to be a mixture of isomers.
[0096]
　(4) Synthesis of transition metal complex (catalyst D)
　under a nitrogen atmosphere, to a 100ml Schlenk tube 8 octamethyl fluorene-12'-yl - (2- (adamantan-1-yl) -8-methyl -3,3B, 4,5,6,7,7A, were charged 8-octahydrocyclopenta [a] indene) 1.039 g, alpha-methyl styrene 0.47 ml, hexane 30 ml, and cyclopentyl methyl ether 2.62 ml. Oil bath under 25 ° C., and the hexane solution 2.18ml of n- butyl lithium 1.6M in this solution was added dropwise over 10 minutes. After stirring for 4 hours at 50 ° C., the precipitate was filtered and washed with hexane to give a pink powder. To 100ml Schlenk tube was charged this pink powder, a diethyl ether 30 ml. The solution was cooled in a dry ice / acetone bath, was added to the solution of zirconium tetrachloride 0.385 g (1.65 mmol) was suspended with diethyl ether 30 ml. Then gradually it stirred for 16 hours while raising the temperature to room temperature.
[0097]
　The solvent was distilled off under reduced pressure, and extracted the soluble matter from the residue with dichloromethane to about 70 ml. After concentrating the resulting extract, hexane was added to 50 ml, was removed insolubles by filtration. The solution was concentrated to about 10 ml, and allowed to stand overnight at -30 ° C.. The precipitated powder was removed by filtration, and washed with hexane to give an orange powder 0.384 g. The orange powder was dissolved by adding diethyl ether 5 ml, and allowed to stand overnight at -30 ° C.. The precipitated powder was taken out by filtration, washed with hexane, the desired product (8 octamethyl fluorene-12'-yl - (2- (adamantan-1-yl) -8-methyl -3,3B, 4, 5,6,7,7a, 8- octahydrocyclopenta [a] indene)) to obtain a zirconium dichloride (catalyst D). Yield 0.220 g, 17% yield.
　 1 the result of the measurement of the H-NMR, was identified the desired product. Measurement results are as follows.
　 1 H-NMR (270 MHz, CDCl 3 , TMS reference): δ7.98 (1H, s) , 7.86 (1H, s), 7.60 (1H, s), 7.37 (1H, s), 6.19 (1H, J = 1.6Hz, d), 5.33 (1H, J = 1.6Hz, d), 3.58-3.44 (2H, m), 2.35-2.28 (1H, m), 2.18 ( 3H, s), 1.94-1.18 (54H, m).
[0098]
[Solid catalyst component preparation]
　under 30 ° C., sufficiently in a three-necked flask equipped with a stirrer 100mL purged with nitrogen, aluminum purified decane 32mL and solid polymethylaluminoxane (manufactured by Tosoh Finechem Corporation) under a stream of nitrogen It was 14.65mmol charged in terms of atom, and a suspension. To the suspension, previously synthesized in the catalyst (D) 50 mg (0.059 mmol in terms of zirconium atom) and a toluene solution of 4.6 mmol / L, was added with stirring the solution 12.75ML. Stirring was stopped after 1.5 hours, the resultant catalyst component was washed 3 times with decane 50mL by decantation, to obtain slurry was suspended in decane (D-2) 50mL. Zr supporting ratio in this catalyst component was 100%.
[0099]
[Prepolymerized catalyst component preparation of]
　the slurry prepared above (D-2), under a nitrogen stream, decane solution of diisobutylaluminum hydride to (2.0 mmol / mL of aluminum atoms terms) 2.0 mL, further 3- methyl-1-pentene was 7.5 mL (5.0 g) charged. Stirring was stopped after 1.5 hours, the resulting prepolymerized catalyst component was washed 3 times with decane 50mL by decantation. The prepolymerized catalyst component was suspended in decane, decane slurry (D-3) 50mL.
[0100]
[Example 1]
(Polymer [X-1])
　at room temperature under a nitrogen stream, made of SUS polymerization vessel in which with a stirrer having an inner volume of 1L, purified decane 425 mL, decane solution (aluminum atom in terms of diisobutylaluminum hydride the in 2.0 mmol / mL) was 0.5 mL (1 mol) charged. Then added 0.0005mmol the prepolymerization catalyst component of the catalyst previously prepared (A) decane slurry (A-2) in terms of zirconium atom was 50NmL charged with hydrogen (first hydrogen loading). Then, it was charged continuously at a constant rate of 4-methyl-1-pentene 250mL to over 2 hours the polymerization vessel. The instrumentation and the polymerization initiator input start time, the temperature was raised to over 0.5 hours 45 ° C. from the start of polymerization, and held for 4 hours at 45 ° C.. Was 90NmL charged hydrogen after 3 hours from the polymerization initiation (the second hydrogen loading). After 4.5 hours from the polymerization initiation, the temperature was lowered to room temperature and after depressurizing to obtain a solid material was immediately filtered a polymer liquid containing a white solid. The solid matter dried under reduced pressure for 8 hours at 80 ° C., to obtain a polymer [X-1]. The yield was 131 g. The results of physical property measurements are shown in Table 1.
[0101]
[Example 2]
(polymer [X-2])
　, a similar reaction except for using Example 1 decane slurry (B-2) in place of the decane slurry (A-2), the polymer [X -2] was obtained 120g. The results of physical property measurements are shown in Table 1.
[0102]
Example 3
(polymer [X-3])
　using decane slurry (C-2) in place of the decane slurry (A-2), except that the polymerization temperature was set to 100 ° C. Similar to Example 1 reaction carried out, the polymer [X-3] was obtained 115g. The results of physical property measurements are shown in Table 1.
[0103]
[Example 4]
(polymer [X-4])
　at room temperature under a nitrogen stream, made of SUS polymerization vessel in which with a stirrer having an inner volume of 1L, purified decane 425 mL, decane solution (aluminum atom in terms of diisobutylaluminum hydride the in 2.0 mmol / mL) was 0.5 mL (1 mol) charged. Then added 0.0005mmol the prepolymerization catalyst component of the catalyst C prepared above decane slurry (C-2) in terms of zirconium atom was 50NmL charged with hydrogen (first hydrogen loading). Then, it was charged continuously at a constant rate to the 4-methyl-1-pentene 250mL and 1-decene 3.3mL mixed solution of over 2 hours the polymerization vessel. The instrumentation and the polymerization initiator input start time, the temperature was raised from the start of polymerization to 30 minutes over 45 ° C., and held for 4 hours at 45 ° C.. Was 90NmL charged hydrogen after 3 hours from the polymerization initiation (the second hydrogen loading). After 4.5 hours from the polymerization initiation, the temperature was lowered to room temperature and after depressurizing to obtain a solid material was immediately filtered a polymer liquid containing a white solid. The solid matter dried under reduced pressure for 8 hours at 80 ° C., to obtain a polymer [X-4]. The yield was 125g. The results of physical property measurements are shown in Table 1.
[0104]
[Example 5]
(polymer [X-5])
　instead of adding a 1-decene 3.3mL as a copolymerizable monomer, the same reaction as in Example 4 except that 1-hexene was added 2.0mL performed, a polymer [X-5] was obtained 115g. The results of physical property measurements are shown in Table 1.
[0105]
[Comparative Example 1]
(Polymer [X'-1])
　of hydrogen charged number and three times in addition to the first hydrogen charged before the start of polymerization as that of Example 1, the polymerization initiator 1 hour after 2 times th hydrogen charging, polymerization initiator 2 hours after subjected to the hydrogen charging of the third, first time, second time, the third time of the hydrogen charging amount except that the 0.5NmL respective same reaction as in example 1 performed, a polymer [X'-1] was obtained 135g. The results of physical property measurements are shown in Table 1.
[0106]
[Comparative Example 2]
(polymer [X'-2])
　of hydrogen charged number and three times in addition to the first hydrogen charged before the start of polymerization as in Example 2, the polymerization initiator 1 hour after 2 times th hydrogen charging, polymerization initiator 2 hours after subjected to the hydrogen charging of the third, first time, second time, a third similar reaction except that the 0.5NmL respectively example 2 hydrogen charging amount of performed, a polymer [X'-2] was obtained 150g. The results of physical property measurements are shown in Table 1.
[0107]
[Comparative Example 3] (polymer [X'-3])
　according to the method of Comparative Example 7 of WO 2006/054613 pamphlet, 4-methyl-1-pentene, 1-decene, changing the ratio of hydrogen to obtain a polymer [X'-3] by. The results of physical property measurements are shown in Table 1.
[0108]
[Comparative Example 4] (polymer [X'-4])
　, a similar reaction except for using Example 4 decane slurry (D-3) instead of decane slurry (C-2), the polymer the [X'-4] was obtained 115g. The results of physical property measurements are shown in Table 1. The results of physical property measurements are shown in Table 1.
[0109]
[Comparative Example 5] (polymer [X'-5])
　of hydrogen charged number and three times in addition to the first hydrogen charged before the same polymerization initiator as in Comparative Example 4, polymerization initiator 1 hour after 2 times th hydrogen charging, perform third hydrogen charged after polymerization initiation 2 hours, first, second, performs the same polymerization reaction as in Comparative example 4 third hydrogen charging amount except that the 50NmL respectively , a polymer was obtained [X'-5]. The yield was 131g.
[0110]

　was optionally be performed multiple times polymerization of the above Examples and Comparative Examples prepared polymer in an amount sufficient to pelletization. For each polymer 100 parts by weight 0.1 parts by weight of tri (2,4-di -t- butyl phenyl) phosphate as a secondary antioxidant, n- octadecyl-3- (4 as a heat-stabilizer '- hydroxy -3', 5'-di -t- butyl phenyl) propionate and 0.1 part by weight. Thereafter, Ltd. Research Laboratory of Plastics Technology Co., Ltd. 2-screw extruder BT-30 (screw type 30 mm?, L / D 46) using a set temperature 260 ° C., the resin extrusion rate 60 g / min and the rotational speed 200rpm conditions in granulated for evaluation was obtained pellets.
[0111]
　To evaluation pellets obtained were subjected to DSC measurement and melt tension measured by the method described later. The results are shown in Table 1.
　Hereinafter, the polymer, the evaluation method of evaluating pellet specifically described. The evaluation results are shown in Table 1.
[0112]
[Configuration unit content]
　at least one olefin selected from 4-methyl-1-pentene polymer of ethylene and carbon atoms 3 ~ 20 alpha-olefin (except 4-methyl-1-pentene) content derived from the structural unit (comonomer) is the following apparatus and conditions, 13 was calculated from the C-NMR spectrum.
[0113]
　Using Bruker BioSpin made AVANCEIIIcryo-500 type nuclear magnetic resonance device, the solvent is o- dichlorobenzene / benzene -d 6 (4/1 v / v) mixed solvent, sample concentration 55 mg / 0.6 mL, measured temperature is 120 ° C., the observed nucleus 13 and C (125 MHz), the sequence a single pulse proton broadband decoupling pulse width 5.0μ sec (45 ° pulse), repetition time 5.5 sec, the integration number 64 times, benzene -d 6 to 128ppm of measured as a reference value for the chemical shift. Using the integral value of the main chain Mechinshigunaru was calculated content of constituent units derived from the comonomer by the following equation.
[0114]
　The content of constituent units derived from the comonomer (%) = [P / ( P + M)] × 100
　where, P is shows the total peak area of the comonomer backbone Mechinshigunaru, M is 4-methyl-1-pentene backbone Mechinshigunaru shows the total peak area of.
[0115]
[Meso diad fraction]
　meso diad fraction of 4-methyl-1-pentene polymer (iso dyads isotacticity -, or also called meso diad isotacticity) are any two head-to-tail in the polymer chain when bound 4-methyl-1-pentene unit chain expressed in planar zigzag structure, defined as the percentage direction are the same for the isobutyl branches, 13 was determined by the following formulas C-NMR spectra.
　Meso diad fraction (iso dyads tacticity) (m) (%) = [m / (m + r)] × 100
(wherein, m, r is the head represented by the following formula - attached at the tail 4- shows the absorption intensity originating from the main chain methylene methyl-1-pentene units.)
[0116]
　 13 C-NMR spectra, using the bulkers BioSpin made AVANCEIIIcryo-500 type nuclear magnetic resonance device, the solvent is o- dichlorobenzene / benzene -d6 (4/1 v / v) mixed solvent, sample concentration 60 mg / 0.6 mL, measurement temperature 120 ° C., the observed nucleus 13 C (125 MHz), the sequence is a single pulse proton broadband decoupling pulse width 5.0μ sec (45 ° pulse), repetition time was 5.5 seconds, was measured 128ppm benzene -d6 as a reference value for the chemical shift.
[0117]
　Peak area, delimiting the region of 41.5 ~ 43.3ppm at the minimum point of the peak profile, high magnetic field side of the first region, were classified downfield in the second region.
　In the first region, 4-methyl-1-but main chain methylene of pentene units 2 in the chain resonates represented by (m), the integrated value regarded as 4-methyl-1-pentene homopolymer "m" and the. In the second region, and resonance 4-methyl-1-backbone methylene pentene units 2 in the chain represented by (r), and the integrated value "r". Incidentally, it was below the detection limit of less than 0.01%.
[0118]
[Mw / Mn, the molecular weight × 10 1 6 ratio of the polymer is not less than]
　weight average molecular weight (Mw) and number-average molecular weight (Mn) were measured by GPC. GPC measurement was carried out under the following conditions. The weight average molecular weight (Mw) and number-average molecular weight (Mn), a calibration curve using commercially available monodisperse standard polystyrene was determined based on the following conversion method.
[0119]
　(Measurement Conditions)
　Apparatus: gel permeation chromatograph HLC-8321 GPC / HT (manufactured by Tosoh Corporation)
　Organic solvent: o-dichlorobenzene
　Column: TSKgel GMH6-HT 2, TSKgel GMH6-HTL columns 2 (both Toso Ltd.)
　flow rate: 1.0 ml / min
　sample: 0.15 mg / mL o-dichlorobenzene solution
　temperature: 140 ° C.
　molecular weight conversion: PS conversion / general-purpose calibration method
[0120]
　Incidentally, the calculation of the general-purpose calibration, using coefficients of Mark-Houwink viscosity equation. Each Mark-Houwink coefficients of PS, literature (J.Polym.Sci., Part A-2,8,1803 (1970)) was used values described.
　Also, among the PS-converted GPC chart, the integrated area value of the molecular weight 1,000,000 or more components, the percentage of the total integrated area charts, molecular weight × 10 1 6 and a ratio of more components.
[0121]
[Melt flow rate (MFR) of]
　the melt flow rate (MFR) 260 ° C. in conformity with ASTM D1238, it was measured under the conditions of 5kg load.
[0122]
[Cold elution quantity (CFC)]
　(Measurement Conditions)
equipment: CFC2 type cross fractionation chromatograph (Polymer Char)
detector (built): IR4 type infrared spectrophotometer (Polymer Char)
Sample concentration: 60 mg / 30 mL
Injection volume : 0.5 mL
mobile phase: o-dichlorobenzene (ODCB), BHT added
flow amount: 1.0 mL / min
[0123]
　Insert the sample prepared by adding a polymer of 60mg respect o- dichlorobenzene (ODCB) 30 mL Device cell, a certain retention time at 145 ° C., to obtain a sample was thoroughly dissolve the polymer. Thereafter, the sample was cooled to 0 ℃ at 1 ° C. / min In order to advance the crystallization, was kept constant time. It was then measured resin amount eluted during the heated sample stepwise at 5 ° C. intervals until 145 ° C. at any time.
　From a result, it calculates the percentage of polymer eluted at 80 ° C. or less to the total polymer was the percentage "cold elution component amount" and (cumulative weight fraction).
[0124]
Mp (Tm), heat of fusion (.DELTA.Hm)]
　using a Seiko Instruments Inc. DSC measurement apparatus (DSC220C), and filled with samples of about 5mg to measurement aluminum pan, was heated to 280 ° C. at 10 ° C. / min. After holding for 5 minutes at 280 ° C., the temperature was lowered to 20 ° C. at 10 ° C. / min. After holding at 20 ° C. 5 min, the temperature was raised to 280 ° C. at 10 ° C. / min. The temperature at which the apex of the observed crystal melting peak during the second Atsushi Nobori appears was taken as the melting point. It was also calculated heat of fusion from the integrated value of the crystal melting peak.
[0125]
Melt tension]
　For the measurement of the melt tension, was used Capirograph 1D is a device Toyo Seiki Seisakusho. Charged sample melting furnace set at 260 ° C. (diameter 9.55 mm), the After sufficient melt, at an extrusion rate of 15mm / min, L / D 8 / 2.095mm, the capillary is entrance angle 180 ° passed, passed through a pulley fixed from the capillary bottom in the position of the 58cm, the molten resin was measured stress on the pulley portion when wound at a speed of 15 m / min, and the stress and melt tension.
[0126]
[Table 1]

WE CLAIM

4-methyl-1-a content of the structural unit derived from pentene 90 to 100 mol%, at least 1 selected ethylene and 4-methyl-1-pentene other α- olefin of 3 to 20 carbon atoms 0-10 mol% content of the constitutional unit derived from species of olefins, meet all the following requirements (a) ~ (f), 4- methyl-1-pentene polymer (X).
(A) 13 meso diad fraction as measured by C-NMR (m) is in the range of less than 98.0% or more 70.0.
(B) measured by gel permeation chromatography (GPC), the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is in the range between 3.6 and 30. FIG.
(C) conforming to ASTM D1238 and 260 ° C., a melt flow rate measured under the conditions of 5kg load (MFR) is in the range of 0.1 ~ 500 g / 10 min.
Was measured by cross fractionation chromatography apparatus using an infrared spectrophotometer in (d) of detector is the amount of the cumulative weight fraction eluting at 80 ° C. less than 5% by weight.
(E) was measured by gel permeation chromatography (GPC), the molecular weight × 10 1 6 ratio of at least the polymer is not less than 15 mass%.
(F) said measured by differential scanning calorimetry (DSC) 4-methyl-1-pentene polymer heat of fusion and the melting point of the following requirements (i) and satisfying the (ii).
　　　　(I) the following formula (1) is satisfied.
　ΔHm <0.5 × Tm-76 ··· Equation (1)
(In the formula (1), the heat of fusion and ΔHmJ / g, a melting point and Tm °
　　　　C..) (Ii) a melting point in the range of 180 ~ 260 ° C..
[Requested item 2]
　4-methyl-1-pentene polymer (X) resin composition containing of claim 1.
[Requested item 3]
　4-methyl-1-pentene polymer (X) or moldings comprising the resin composition according to claim 2 of claim 1.
[Requested item 4]
　An injection molded article or extrusion molded product, the molded body according to claim 3.
[Requested item 5]
　A film, molded product according to claim 3.
[Requested item 6]
　A blow molded article, molded article according to claim 3.