Technical field
[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 like or release film composite material molding, or chemical resistance, water resistance, transparency taking advantage of the features such as are used, for example in laboratory instruments and rubber hose manufacturing mandrel.
[0003]
　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).
[0004]
　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
[0005]
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
[0006]
　As described above, the 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, but has excellent features in heat resistance , according to the study of the present inventors, the relative shaped bodies using steam sterilization, i.e. that there are cases where turbidity and performing steam sterilization occurs was found. A required steam sterilization, and in applications where transparency or appearance is important, it is a problem that white turbidity occurs.
[0007]
　The film obtained from 4-methyl-1-pentene polymer described in Patent Documents 3 and 4 have excellent characteristics in heat resistance, etc. However, according to the study of the present inventors, the elongation of the film There may be insufficient, that there is a case that is likely to cause a film out at the time of film take-up has been found.
[0008]
　The present invention is an object to solve the above problems of the prior art. That object of the present invention is to suppress the clouding during steam sterilization without resulting molded article to impair the characteristics such as high heat resistance of the above 4-methyl-1-pentene polymer, further, the without impairing the 4-methyl-1-properties such as high heat resistance pentene polymer is to improve the elongation of the resulting film.
Means for Solving the Problems
[0009]
　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.
[0010]
　The present invention relates to the following [1] to [9].
[1] The content of the constitutional unit derived from 4-methyl-1-pentene is 90 to 100 mol%, selected from ethylene and 3 to 20 carbon atoms 4-methyl-1-pentene other α- olefin content of at least one constituent unit derived from olefins is 0 to 10 mol%, satisfies all the following requirements (a) ~ (e), 4- methyl-1-pentene polymer.
(A) 13 meso diad fraction as measured by C-NMR (m) is in the range 98 to 100%.
(B) measured by gel permeation chromatography (GPC), the ratio of the Z average molecular weight Mz and the weight average molecular weight Mw (Mz / Mw) is in the range of 2.5-20.
(C) were 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.
(D) conforms 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.
(E) 23 ° C. decane soluble part amount is more than 5.0 mass%.
[0011]
[2] In addition 4-methyl-1-pentene polymer according to the following requirements satisfy (f) [1].
(F) were measured by gel permeation chromatography (GPC), the molecular weight × 10 1 6 ratio of at least the polymer is not less than 15 mass%.
[3] In addition the following requirement satisfies the (g) [1] or 4-methyl-1-pentene polymer according to [2].
(G) filling the is measured by differential scanning calorimetry (DSC) 4-methyl-1-pentene polymer heat of fusion and the melting point of the following requirements (i) and (ii).
[0012]
　　　　(I) the following formula (1) is satisfied.
[0013]
　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 200 ~ 260 ° C. It is in.
[4] [1] to [3] a resin composition containing a 4-methyl-1-pentene polymer according to any one of.
[0014]
[5] [1] ~ shaped body comprising the resin composition described in [3] 4-methyl-1-pentene polymer or according to any one of [4].
[6] the maximum thickness is at less than 100mm, molded article according to the minimum thickness is not less than 0.001 mm [5].
[0015]
[7] is an injection molded article or extrusion molded product, molded article according to [5] or [6].
[8] a film, molded article according to [5].
[9] [5] - [8] Medical is a molded body according to any one, nursing, infants, for physics and chemistry experiments, food, living or instruments or containers for chemicals.
Effect of the invention
[0016]
　According to the present invention, a high and a stereoregularity and a high heat of fusion, moreover molded body that can suppress the occurrence of white turbidity even when the steam sterilization is obtained 4-methyl-1-pentene polymer and it is possible to provide a resin composition. Furthermore, the use of the 4-methyl-1-pentene polymer and a resin composition of the present invention has heat resistance, rigidity, yet can provide a molded article such as a film excellent in elongation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017]
[1] Figure 1 is in the examples and comparative examples is a graph showing the relationship between heat of fusion and the melting point.
DESCRIPTION OF THE INVENTION
[0018]
　Hereinafter, according to the present invention 4-methyl-1-pentene polymer, detailing the resin composition containing a polymer, and for the polymer and a molded body including a resin composition.
[0019]
　<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 90 to 100 mol% content of the constitutional unit derived from pentene, at least one olefin selected from ethylene and 3 to 20 carbon atoms 4-methyl-1-pentene other α- olefin (hereinafter, also referred to as a comonomer) content of the constitutional unit derived from is 0 to 10 mol%, satisfies the following requirements (a) ~ (e), preferably further following requirement (f) and one or more of the (g) Fulfill. 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) ~ (e) satisfies the means preferably satisfies one or more of further requirement (f) and (g).
[0020]
　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.
[0021]
　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%.
[0022]
　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.
[0023]
　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).
[0024]
　The following describes each requirement that 4-methyl-1-pentene polymer (X) satisfies.
(Requirement (a))
　 13 is in the range meso diad fraction as measured by C-NMR (m) is 98 to 100%, preferably in the range 98.5 to 100 percent.
[0025]
　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.
[0026]
　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.
(Requirement (b))
　was measured by gel permeation chromatography (GPC), the ratio of the Z average molecular weight Mz and the weight average molecular weight Mw (Mz / Mw) is in the range of 2.5 to 20, preferably 2. 5-15, and more preferably 2.7 to 15, more preferably in the range of 2.8 to 15. The ratio (Mz / Mw) is that 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 (Mz / Mw) in the above range, 4-methyl-1-pentene polymer (X) larger polymer having a molecular weight in suggesting that contained significant amounts. How the ratio of (Mz / Mw) is adjusted to the above range will be described later in detail.
[0027]
(Requirement (c))
　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 it is 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.
[0028]
(Requirement
　(d)) 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.
[0029]
　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.
[0030]
　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.
(Requirement
　(e)) 4-methyl-1-pentene polymer (X) is, 23 ° C. decane-soluble component quantity is not more than 5.0 wt%, preferably 3.0 wt% or less, more preferably 1.0 mass% or less.
[0031]
　In the present invention, the 23 ° C.-decane soluble part amount, as detailed in the Examples below, was added 4-methyl-1-pentene polymer (X) in n- decane at 145 ° C. 1 after dissolved by heating time, n- decane solution definitive when the temperature was lowered to 23 ° C., and relative to the weight of the added polymer (X), n- decane solution dissolved in it are polymer ratio of the weight of (X) show.
[0032]
　4-methyl-1-be 23 ° C. decane soluble part amount of pentene polymer (X) is small, indicating that the amount of low molecular weight polymer contained in the polymer (X) is small. By 23 ° C. decane soluble part amount of 4-methyl-1-pentene polymer (X) is within the above range, the low molecular weight as a contaminant from the molded product obtained from a resin composition containing the polymer since it is possible to suppress the outflow of the components, it can be suitably used in such applications of the film which is required high purity.
[0033]
　In the present invention, 23 ° C. decane soluble part amount of 4-methyl-1-pentene polymer (X) can be adjusted by the type of olefin polymerization catalyst described below.
(Requirement (f))
　were 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 is 17 mass% or more. By the above range, molded bodies such as films, including 4-methyl-1-pentene polymer (X) is as excellent toughness, internal cracks are reduced is the cause of whitening, excellent in film elongation . The molecular weight × 10 1 6 the proportion of the of the polymer than in the above range suggests 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, by increasing or decreasing the amount, It can be adjusted in the above range.
[0034]
(Requirement (g))
　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).
[0035]
　　　　(I) the following formula (1) is satisfied.
[0036]
　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 200 ~ 260 ° C. It is in.
[0037]
　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 200 ~ 250 ° C., more preferably 205 to 250 ° C., more preferably from 210 ~ 245 ° C..
[0038]
　Above requirements (i), according to the present invention 4-methyl-1-pentene polymer (X) is shown to have a high heat of fusion. Specifically, according to the present invention 4-methyl-1-pentene polymer (X) has a heat of fusion for a large melting point, i.e., the feature of high crystallinity. As an example showing the relationship between the heat of fusion and the melting point, shown in Figure 1 the relationship between the heat of fusion and the melting point in the examples and comparative examples of the present invention to be described later.
[0039]
　Note for this requirement contains detailed disclosed in Patent Document 3, there is similarly disclosed in the patent document 4. 4-methyl-1-pentene polymer disclosed in Patent Documents 3 and 4 also satisfy this requirement. Comparative Example 1 described later meets this requirement, Comparative Examples 2 and 3 does not satisfy this requirement.
[0040]
　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 of the present invention, as evident from comparison of examples and comparative examples described below, the steam sterilization after cloudiness even has a difficult characteristic generating. In Comparative Example, although the reason is not clear resulting cloudy by steam sterilization, moisture enters the inside of the molded body during sterilization, expanded, micro cracks distortion occurs during shrinkage of the molded body due to cooling after sterilization It is presumed that has occurred.
[0041]
　As residual strain due to molding such as injection molding is large, the above micro-cracks are likely to occur usually considered, also the residual strain is better to contain many components of high molecular weight in the polymer is is a normal large is there. Nevertheless, in the 4-methyl-1-pentene polymer of the present invention it is estimated that occurrence of microcracks is greatly suppressed, an unexpected effect. By including substantial amounts of high molecular weight component, improvement in toughness is caused by entanglement number per unit volume is increased, it is considered that it would be whitening is suppressed.
[0042]
　Further, 4-methyl-1-pentene polymer of the present invention because it is high crystallinity, when formed into a film is also concerned that the physical properties is reduced, with more components of high molecular weight in the polymer Those who contain the higher the orientation, it is usually the film elongation is lowered. Nevertheless, it is observed significant improvement in film elongation unexpectedly in 4-methyl-1-pentene polymer of the present invention. Again by containing substantial amounts of high molecular weight component, the entanglement number per unit volume is estimated to effect of toughness is improved by increasing.
[0043]
<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.
[0044]
　 [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) compound react to form an ion pair
　at least one compound selected from (B), and catalysts comprising preferred.
[0045]
　
　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.
[0046]
[Formula 1]

[0047]
　Wherein [A1], M is a Group 4 of the periodic table transition metals, such as titanium atom, a zirconium atom or a hafnium atom, Q is a halogen atom, a hydrocarbon group, conjugated or nonconjugated diene of the following neutral 10 carbon atoms is selected in the same or different combination from a neutral ligand capable of coordination with an anionic ligand and a lone pair, j is an integer of 1 ~ 4, R a and R B are either the same or different from each other at best, 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 , which 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.
[0048]
[Formula 2]

[0049]
　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-containing hydrocarbon group is selected from, respectively may be the same or different, each substituent may be bonded to each other to form a ring. M is a transition metal of Group 4 of the periodic table, Q is a halogen atom, a hydrocarbon group, can be coordinated neutral conjugated or nonconjugated diene, anionic ligand and lone pair having 10 or less neutral carbon chosen by the same or different combination from ligand, j is an integer of 1-4.
[0050]
　Among the bridged metallocene compound represented by the general formula [A2], the polymerization properties, availability, in terms of obtaining a polymer satisfying the above requirements, cross-linked metallocene compound represented by the general formula [A3] are particularly preferred.
[0051]
[Formula 3]

[0052]
　Wherein [A3], R 1b is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, R 2b ~ R 12b is a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group is selected from, respectively may be the same or different, each substituent may be bonded to each other to form a ring. M is a transition metal of Group 4 of the periodic table, n is an integer of 1 ~ 3, Q is a halogen atom, a hydrocarbon group, conjugated or nonconjugated diene neutral having 10 or less carbon atoms, an anionic ligand and chosen by the same or different combination from a neutral ligand capable of coordination by lone pair, j is an integer of 1-4.
[0053]
　 　R 1 from R 10 and R 1b R from 12b as the hydrocarbon group in, for example, linear hydrocarbon groups, branched hydrocarbon groups, cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group include substituted and formed by groups one or more hydrogen atom of the saturated hydrocarbon group cyclic unsaturated hydrocarbon group. The carbon number of the hydrocarbon group is usually 1 to 20, preferably 1 to 15, more preferably 1 to 10.
[0054]
　Examples of the straight chain hydrocarbon group, such as methyl group, ethyl group, n- propyl group, n- butyl group, n- pentyl group, n- hexyl, n- heptyl, n- octyl, n- nonyl It includes straight-chain alkenyl groups such as allyl group; group, a linear alkyl group such as n- decanyl group.
[0055]
　Examples of the branched hydrocarbon group, for example, isopropyl, tert- butyl group, tert- amyl group, 3-methylpentyl group, 1,1-diethyl propyl group, 1,1-dimethylbutyl group, 1-methyl-1 - propyl butyl group, 1,1-propyl butyl group, 1,1-dimethyl-2-methylpropyl group, and a branched alkyl group such as 1-methyl-1-isopropyl-2-methylpropyl group.
[0056]
　The cyclic saturated hydrocarbon group, such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, a cycloalkyl group such as a methyl cyclohexyl group; norbornyl group, adamantyl group, polycyclic group such as a methyl adamantyl group It is.
[0057]
　The cyclic unsaturated hydrocarbon group include a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group, an aryl group such as an anthracenyl group; a cycloalkenyl group such as cyclohexenyl group; 5- bicyclo [2.2. 1] unsaturated polycyclic alicyclic group, such as hept-2-enyl group.
[0058]
　The one or more hydrogen atoms formed by replacing the cyclic unsaturated hydrocarbon group groups of the saturated hydrocarbon group, for example, a benzyl group, cumyl group, 1,1-diphenylethyl group, triphenylmethyl group and the like one or more hydrogen atoms with alkyl groups can be mentioned a group formed by substituting an aryl group.
[0059]
　R 1 from R 10 and R 1b R from 12b as the silicon-containing groups in, for example, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, the formula -SiR such triphenylsilyl group 3 (wherein , the plurality of R include groups represented by each independently an alkyl group or a phenyl group having 1 to 15 carbon atoms.).
[0060]
　R 1 from R 10 and R 1b R from 12b as the halogen-containing hydrocarbon group in, for example, formed by substitution, such as trifluoromethyl group, one or more hydrogen atom of the above hydrocarbon groups by a halogen atom group, and the like.
[0061]
　R 2 from R 10 and R 2b from R 12b as the halogen atom in, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.
[0062]
　R 2 from R 10 and R 2b from R 12b of substituents up to two substituents (eg: R 2b and R 3b , R 3b and R 4b , R 5b and R 6b , R 6b and R 7b , R 8b and R 9b , R 9b and R 10b , R 10b and R 11b , R 11b and R 12b ) is may be bonded to each other to form a ring, wherein said ring formation, two places in the molecule
exist or it may be.
[0063]
　In the present invention, the ring two substituents bonded to formed together (spiro ring, additional rings), for example, alicyclic, and aromatic ring. Specifically, cyclohexane ring, benzene ring, hydrogenated benzene ring, include a cyclopentene ring, preferably a cyclohexane ring, a benzene ring and hydrogenated benzene ring. Moreover, such ring structures may further have a substituent of an alkyl group on the ring.
[0064]
　R 1b , from the viewpoint of stereoregularity is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably not aryl groups, linear hydrocarbon group, especially preferably a branched hydrocarbon group, or a cyclic saturated hydrocarbon group, particularly a carbon having a free valence (carbon bonded to the cyclopentadienyl ring) is a substituent a tertiary carbon preferable.
[0065]
　R 1b as, specifically, a methyl group, an ethyl group, an isopropyl group, tert- butyl group, tert- pentyl, tert- amyl group, 1-methylcyclohexyl group, can be exemplified 1-adamantyl group, more preferably the tert- butyl group, tert- pentyl, 1-methylcyclohexyl group, a substituent carbon is a tertiary carbon bearing a free valence and 1-adamantyl group, particularly preferably tert- butyl group, 1- adamantyl group.
[0066]
　In the general formula [A3], fluorene ring portion is not particularly limited as long as the structure derived from known fluorene derivatives, R 4b and R 5b are stereoregular, in terms of molecular weight, preferably a hydrogen atom.
[0067]
　R 2b , R 3b , R 6b and R 7b is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms. Also, R 2b and R 3b are bonded to each other to form a ring, and R 6b and R 7b may form a ring by bonding to each other. As such substituted fluorenyl group, for example, benzofluorenyl group, dibenzo fluorenyl group, octahydro-dibenzo fluorenyl group, 1,1,4,4,7,7,10,10- octamethyl -2 , 3,4,7,8,9,10,12- octahydro -1H- dibenzo [b, h] fluorenyl group, 1,1,3,3,6,6,8,8- octamethyl-2,3, 6,7,8,10- hexahydro -1H- dicyclopenta [b, h] fluorenyl group, 1 ', 1', 3 ', 6', 8 ', 8'-hexamethyl-rH, 8'H- dicyclopenta [b, h] fluorenyl group, and particularly preferably 1,1,4,4,7,7,10,10- octamethyl -2,3,4,7,8,9,10,12- octahydro - is 1H- dibenzo [b, h] fluorenyl group.
[0068]
　R 8b is preferably is a hydrogen atom.
[0069]
　R 9b is more preferably is a hydrocarbon group, R 9b represents a linear alkyl group, branched alkyl alkyl group having 2 or more carbon atoms such as a group, more preferably a cycloalkyl group or cycloalkenyl group, R 9b is especially preferred is alkyl group having 2 or more carbon atoms. In view of synthesis, R 10b and R 11b also preferably is a hydrogen atom.
[0070]
　Alternatively, if it is n = 1, R 9b and R 10b is more preferably are bonded to each other to form a ring, it is particularly preferred the ring is a 6-membered ring such as cyclohexane ring. In this case, R 11b is preferably is a hydrogen atom.
[0071]
　R 12b is preferably a hydrocarbon group, particularly preferably an alkyl group.
[0072]
　
　M is a transition metal of Group 4 of the periodic table, such as Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Zr.
[0073]
　Q represents a halogen atom, a hydrocarbon group, conjugated or nonconjugated diene of the following neutral 10 carbon atoms, and a neutral ligand capable of coordination by an anionic ligand or a lone pair of electrons.
　The halogen atom in Q, for example, fluorine, chlorine, bromine, and iodine.
[0074]
　The hydrocarbon group in Q, alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms preferably. Examples of the alkyl group having 1 to 10 carbon atoms, a methyl group, an ethyl group, n- propyl group, iso- propyl, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1 , 1-diethyl-propyl, 1-ethyl-1-methylpropyl group, 1,1,2,2-methylpropyl group, sec- butyl group, tert- butyl group, 1,1-dimethylbutyl group, 1, 1,3-trimethyl-butyl group, a neopentyl group and the like; the cycloalkyl group having 3 to 10 carbon atoms, a cyclohexylmethyl group, a cyclohexyl group, 1-methyl-1-cyclohexyl groups. Number of carbon atoms in the hydrocarbon group is more preferably 5 or less.
[0075]
　The conjugated or non-conjugated diene having 10 or less of neutral atoms, s- cis - or s- trans eta 4 -1,3-butadiene, s- cis - or s- trans eta 4 -1,4- diphenyl-1,3-butadiene, s- cis - or s- trans eta 4 -3-methyl-1,3-pentadiene, s- cis - or s- trans eta 4 -1,4-dibenzyl-1, 3-butadiene, s- cis - or s- trans eta 4 -2,4-hexadiene, s- cis - or s- trans eta 4 -1,3-pentadiene, s- cis - or s- trans eta 4 -1,4-ditolyl-1,3-butadiene, s- cis - or s- trans eta 4 -1,4-bis (trimethylsilyl) -1,3-butadiene and the like.
[0076]
　Examples of the anionic ligand, methoxy, alkoxy group such as a tert- butoxy; aryloxy groups such as phenoxy; acetate, carboxylate groups benzoate and the like; mesylate, sulfonate groups tosylate, etc. are exemplified.
[0077]
　The neutral ligands capable of coordination by lone pair, trimethylphosphine, triethylphosphine, triphenylphosphine, organic phosphorus compounds such as diphenyl methyl phosphine; tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-dimethoxyethane ethers such as ethane and the like.
[0078]
　Q preferred embodiment is a halogen atom or an alkyl group having 1 to 5 carbon atoms.
[0079]
　n is an integer of 1 to 3, preferably 1 or 2, more preferably 1. By n is the value from the viewpoint of obtaining the resulting polymer efficiently.
[0080]
　j is an integer of 1 to 4, preferably 2.
[0081]
　The structures of the general formula [A2] or a crosslinking metallocene compound represented by the [A3], i.e. R 1 ~ R 10 , R 1b ~ R 12b , M, n, for Q and j, have been described preferred embodiments. In the present invention, any combination of respective preferred embodiments is also a preferred embodiment. Such bridged metallocene compounds can be suitably used to obtain a polymer of the present invention having the above properties.
[0082]
　The bridged metallocene compound represented by the general formula [A3], (8- octamethyl fluorene-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-tetramethyl-fluorene) 12'-yl - (2- (adamantane -1 - yl) -8-methyl -3,3b, 4,5,6,7,7a, 8- octahydrocyclopenta [a] indene)) zirconium dichloride is particularly preferred. Here, the octamethyl fluorene 1,1,4,4,7,7,10,10- octamethyl -2,3,4,7,8,9,10,12- octahydro -1H- dibenzo [b , is that of h] fluorene.
[0083]
　
　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 (hereinafter referred to as "compound (B)".)
preferably contains a.
[0084]
　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, it is applicable example of disclosed in JP 2015-74645.
[0085]
　
　olefin polymerization catalyst is more preferably further comprises a carrier (C).
[0086]
　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).
[0087]
　
　　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.
[0088]
　 4-methyl-1-ratio pentene polymer (X) (Mz / Mw) and the ratio (Mw / Mn) of a single-stage or in multi-stage polymerization method such as two-stage polymerization, it can be adjusted by blending in polymerizing different polymer molecular weight or after polymerization.
[0089]
　In Examples 1 and 2 of the present invention, while a single-stage polymerization, the ratio by dividing the hydrogen introducing the "initial stage of polymerization" and "polymer production middle" (Mz / Mw) and ( Mw / Mn) of which was adjusted to an arbitrary value, adjustment is also possible by such a method. 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 (Mz / Mw) and the (Mw / Mn).
[0090]
<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.
[0091]
[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.
[0092]
　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%.
[0093]
　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.
[0094]
　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 polyurethanes, vinyl chloride resins, vinylidene chloride resins, acrylic resins, ethylene-vinyl acetate copolymer, ethylene methacrylate acrylate copolymers; ionomers, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, fluorine-based resins polycarbonates; polyacetals; Po 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, polyisobutylene rubber, natural rubber, silicone rubber and the like.
[0095]
　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.
[0096]
　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.
[0097]
　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.
[0098]
　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.
[0099]
　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.
[0100]
　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.
[0101]
　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.
[0102]
　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.
[0103]
　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) molecular weight is preferably in the range of about 100 to 10,000. Rosin resin, terpene resin and petroleum resin can be used commercially.
[0104]
　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.
[0105]
　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.
[0106]
　The thermoplastic resin (E), can either be used alone one from among the thermoplastic resins, may be used in combination of two or more thereof.
[0107]
　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.
[0108]
　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.
[0109]
　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, be mentioned methacrylic resin powder, etc. it can. Among these, silica fine powder and crosslinked acrylic, methacrylic resin powder are preferred.
[0110]
　As the pigment, inorganic content (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.
[0111]
　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.
[0112]
　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.).
[0113]
　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.
[0114]
　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.
[0115]
　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.
[0116]
　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.
[0117]
　As the ultraviolet absorber, benzotriazole-based, benzophenone-based, salicylic acid-based, acrylate-based, and the like.
[0118]
　Antibacterial agents, quaternary ammonium salts, pyridine based compounds, organic acids, organic acid esters, halogenated phenol, and organic iodine.
[0119]
　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 and the like, as an anionic surfactant is, 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 sulfonate, Include a phosphoric acid ester salts such as grade alcohol phosphate ester salt, the cationic surfactants, such as quaternary ammonium salts such as alkyl trimethyl ammonium salts. Examples of the amphoteric surfactant, higher alkyl amino acid salts amino acid type duplex surfactants such as higher alkyl dimethyl betaines, such as betaine type amphoteric surfactants such as higher alkyl time hydroxyethyl betaine.
[0120]
　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.
[0121]
　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.
[0122]
<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 it is 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.
[0123]
　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.
[0124]
　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) .
[0125]

　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.
[0126]
(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.
[0127]
　The clouded by steam sterilization, it is observed tendency noticeable the larger the thickness of the molded body. Further, the molded article has thicker portions may not be sufficiently suppressed clouding the improving effect according to the present invention. From this viewpoint, the thickness of the minimum thickness portion of the shaped body is preferably 0.001mm or more, more preferably 0.01mm or more, more preferably 0.05mm or more and maximum wall of the molding the thickness of the thick portion is preferably 100mm or less, more preferably less than 50mm, more preferably 6mm or less, more preferably less than 3mm. Here, the wall thickness A, the plates distance molded body when sandwiched between parallel plates, if massive, tubular, film, sheet, membrane, tape-like, its thickness if plate , rod-like, refers to its thickness if fibrous. If the wall thickness distribution in the molded body is present, the thickness of the minimum thickness portion of the maximum value maximum thickness portion of the thickness, the minimum value. Method of measuring the wall thickness, and a method for measuring for example the cross section of the shaped body with calipers.
[0128]
　In the following, the film is a general term for planar moldings, sheets, and concept including a tape.
(3) Use
　the molded body of the present invention is conventional 4-methyl-1-pentene polymer may be employed without limitation in applications that may be used, more in applications requiring heat resistance and low contamination Is suitable. Also a characteristic of the present invention may from clouding inhibiting effect by steam sterilization, or applications involving sterilization process with steam, is used as a molded article obtained through the sterilization process with steam. More specific applications, medical devices, medical packaging materials, laboratory equipment, there is a cosmetic containers, baby supplies, food containers, container and equipment for microwave steam sterilization.
[0129]
　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.
[0130]
　The Applications of the molded body according to the present invention set forth below, but not particularly limited to.
[0131]
　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.
[0132]
　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.
[0133]
　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 cells, batteries sebacate aerator, Sebareta for lithium ion batteries, fuel cell electrolyte membrane, an adhesive-adhesive Sebareta, light guide plate, an optical disk, a dicing tape back grinding tape die bonding film, two-layer FCCL, substrate-adhesive-Sebareta for a semiconductor process films such as films capacitor films, adhesive films, stress relaxation film, a pellicle film, a polarizing plate film, a protective film for a polarizing plate, The protective film for liquid product 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, baked for Irumu, masking film, capacitor film, the capacitor film, the tab lead film, a fuel cell capacitor film, reflective film, diffusion film, laminate (including glass), radiation-resistant film, resistance to γ-ray film, a protective film such as a porous film, heat dissipation film sheet, the sealed electronic component manufacturing mold, LED mold, high-frequency circuit laminates, high-frequency cable covering material, the optical waveguide substrate, glass fiber composites, carbon fiber composites, glass intermediate films, laminated glass use films, building materials for window film, arcade dome, gymnasium glazing alternative, an LCD substrate film, bulletproof materials, bulletproof glass films, heat shielding sheet, heat insulating film, if skin for release paper, advanced composite material for release paper, carbon fiber composite curing release paper, glass fiber composite curing release paper, Aramid fiber composite curing release paper, nanocomposite curing release paper, release paper, such as filler filler curing release paper, heat water printing paper, packaging films, release films, breathable films, reflective films, synthetic paper, display films, display conductive film, such as a display barrier film.
[0134]
　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, Eada Tohosu, 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 grommets Bok, suspension cover boots, glass guide, inner belt line seal, the roof guide, trunk lid seals, molded quarter window gaskets, corner Mall Day packaging, 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, motor vehicles, such as seat adjusters cover Interior and exterior material, damping tires, 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, Enpuremu, air filter packing, connectors for automobiles evening, ignition coil, switch, lamp reflector, relay, electric control unit case, sensor housing, headlamps, meter plate, 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, footwear, apparel, bags, covering materials 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 for the seat, the water stopping material, joint material, gasket, door , door frames, window frames, Mawarien, baseboards, opening frame or the like, flooring, ceiling material, wallpaper, health supplies (for example, non-slip mat sheet, fall prevention film, Matt sheet), health equipment member, shock absorbent pad, the protector protective equipment (eg helmet, guard), sporting goods (for example: Sports grip, protector), sports armor, racket, mouth guard, ball, golf ball, transport equipment (for example: transport for shock absorption Guriffu, impact-absorbing sheet), the damping pallet, shock-absorbing damper, insulator, for footwear shock absorber, shock absorbing foams, shock absorbing film and sheet Shock absorbing material such as a grip material (writing instrument, tool, sporting 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, the heater pump spout-outlet, the IH rice cooker, rice cookers in the lid, oven rollers stay ring, cleaner fan guide, electronic jar use pump filter case, garbage disposal parts, the processing tank and heating dry parts, milk meters, filter bowls, escalator parts, an ultrasonic motor housing, absolute encoders, miniature pump housing, TV member, hair dryer housing, light cover, miscellaneous goods, coffee dripper, humidifier parts, eye Down parts, water supply equipment parts, water bottle, comb, fountain pen, pencil, pencil sharpener, sports leisure goods, ski goggles, karate, kendo armor, surfing fins, musical instruments, fish tank, sandals, shoveling snow shovel, fishing rod case, toys, shoes bottom, the bottom sole, shoe midsole, inner sole, sole, sandals, chair skin, bags, 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 mats, electric tool member, farm equipment member, heat dissipating material, a transparent substrate, acoustic insulation, sound-absorbing material, cushion material, wire cable, shape memory materials, connectors, switches, plugs, appliance parts (motor parts, housings, etc.), medical gaskets, spin Ca diaphragm, medical cap, Kusurisen, gaskets, was filled with 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 material , industrial sewing machine table, license plate housing, cap liner, such as a pET bottle 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, audio precision equipment, OA equipment support member, such as a vibration-proof material, 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 an optical media, an optical measuring cell, costume case, clear Over scan, 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 fabric or cloth diapers , sanitary goods, sanitary goods, a filter, a 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 film, the heart-lung machine, injection 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, protective glasses, IC carrier, pickup lenses, burn in socket, and the like.
[0135]
　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.
[0136]
　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, as a resin additive to automotive parts, parts for household products, waxes, greases, engine oils, fine ceramics, plating, etc. It can also be used as a resin additive.
Example
[0137]
　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 of transition metal
　complex] (8-octamethyl fluorene-12'-yl - (2- (adamantan-1-yl) -8-methyl -3,3b, 4,5,6,7,7a, 8- synthesis of octahydrocyclopenta [a] indene)) zirconium dichloride (catalyst a)
　(1) 1-synthesis of adamantyl cyclopentadienyl lithium
　under a nitrogen atmosphere, to a 200ml three-necked flask ethylmagnesium bromide 1.0M concentration tert- It was charged with butyl methyl ether solution 40 ml. The solution was cyclopentadiene 2.64g was added dropwise over 20 minutes while cooling in an ice bath, and stirred for 17 hours cooled to room temperature, the solution A was prepared.
[0138]
　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 A prepared above for 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.
[0139]
　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.
[0140]
　 1 the result of the measurement of the H-NMR, was identified the desired product. Measurement results are as follows.
[0141]
　 1Ｈ－ＮＭＲ（ＴＨＦ－ｄ 8）：δ５．５７－５．５５（２Ｈ，ｍ），５．５２－５．５０（２Ｈ，ｍ），１．９６（３Ｈ，ｓ），１．８７（６Ｈ，ｓ），１．７４（６Ｈ，ｓ）．
[0142]
(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, was 47% yield.
[0143]
　 1 H-NMR, the measurement results of GC-MS, was identified the desired product. Measurement results are as follows.
[0144]
　 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).
　MS-GC: M / Z = 306 (M Tasu ).
　(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.
[0145]
　The measurement results of FD-MS, was identified the desired product. Measurement results are as follows.
[0146]
　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.
[0147]
　(4) Synthesis of transition metal complex (catalyst A)
　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, it 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.
[0148]
　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, to give 8-octahydrocyclopenta [a] indene)) zirconium dichloride. Yield 0.220 g, 17% yield.
[0149]
　 1 the result of the measurement of the H-NMR, was identified the desired product. Measurement results are as follows.
[0150]
　 1Ｈ－ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ 3，ＴＭＳ基準）：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）．
[0151]
[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 (A) 50 mg (0.059 mmol in terms of zirconium atom) and a toluene solution of 4.6 mmol / L, it was added with stirring the solution 12.75ML. Stirring was stopped after 1.5 hours, the catalyst component obtained was washed 3 times with decane 50mL by decantation method to obtain suspended in decane slurry solution (B) 50mL. Zr supporting ratio in this catalyst component was 100%.
[0152]
[Prepolymerized Preparation of catalyst component]
　in the slurry liquid prepared in the above (B), under a nitrogen stream, decane solution of diisobutylaluminum hydride (2.0 mmol / mL of aluminum atoms terms) 2.0 mL, further 3-methyl - 1-pentene was 7.5mL (5.0g) 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) 50 mL. The concentration of the prepolymerized catalyst component in decane slurry (C) is 20 g / L, a 1.05mmol-Zr / L, Zr recovery was 90%.
[0153]
[Example 1] (Polymer [A-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 decane slurry solution of prepolymerized catalyst component prepared above and (C) 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 [A-1]. The yield was 131g. Of the polymer [A-1] 13 C-NMR, GPC, the results of MFR and decane soluble part measurements are shown in Table 1.
[0154]
[Example 2] (polymer [A-2])
　except for using 1.3ml of 1-decene charging amount, the same polymerization reaction as in Example 1, to obtain a polymer [A-2] It was. The yield was 125g. Of the polymer [A-2] 13 C-NMR, GPC, MFR and decane soluble part measurement results are shown in Table 1.
[0155]
Example 3 (polymer
[A-3]) (1) Synthesis of Polymer [A-3-1]
　hydrogen charging times and a total of 3 times, the first time before the same polymerization initiator as in Example 1 in addition to the hydrogen charging, polymerization initiator 1 hour after the second hydrogen charging, polymerization initiator 2 hours after subjected to the hydrogen charging of the third, first, second, and each third hydrogen charging amount 60NmL except that the performs the same polymerization reaction as in example 1, a polymer was obtained [a-3-1]. The yield was 126g. Of the polymer [A-3-1] 13 C-NMR, GPC, MFR and decane soluble part measurement results are shown in Table 1.
[0156]
(2) Synthesis of Polymer [A-3-2]
　1 time, second time, except that the third hydrogen charging amount respectively and 35NmL performs the same polymerization reaction as polymer [A-3-1] , obtain a polymer [a-3-2]. The yield was 126g. Of the polymer [A-3-2] 13 C-NMR, GPC, the results of MFR and decane soluble part measurements are shown in Table 1.
[0157]
(3) polymer [A-3] Preparation of
　a polymer [A-3-1] and the polymer [A-3-2], the polymer [A-3-1] 65, the polymer [A- 3-2] was obtained sufficiently combined with the polymer in 35 mass ratio of [a-3]. Of the polymer [A-3] 13 C-NMR, GPC, the results of MFR and decane soluble part measurements are shown in Table 1.
[0158]
[Comparative Example 1] (Polymer [B-1])
　1 time, second time, except that the third hydrogen charging amount respectively and 50NmL performs the same polymerization reaction as polymer [A-3-1] , a polymer was obtained [B-1]. The yield was 131g. Of the polymer [B-1] 13 C-NMR, GPC, the results of MFR and decane soluble part measurements are shown in Table 1.
[0159]
[Comparative Example 2] (polymer [C-1]) and [Comparative Example 3] (polymer [C-2])
　The polymer [C-1] and [C-2] is, WO 2006/054613 each pamphlet, was obtained by an analogous procedure to Comparative examples 7 and 9, changing 4-methyl-1-pentene, 1-decene, 1-hexadecene, 1-octadecene, the percentage of hydrogen. 13 C-NMR, GPC, the results of MFR and decane soluble part measurements are shown in Table 1.
[0160]

　the polymerization as required by a plurality of times to prepare the 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.
[0161]
　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.
[0162]

　to prepare a press sheet by thermally pressing the evaluation pellets by hot pressing machine. Two sheets of brass plates and spacer scissors for evaluation pellets, to produce a press sheet by press this. By changing the thickness of the spacer as appropriate to obtain a pressed sheet of the desired thickness. Hot pressing, after holding until the resin is completely melted at 270 ° C., 100KG / cm 2 for 3 minutes pressed under the conditions of, then immediately 20 ° C., 100KG / cm 2 was performed by pressing for 3 minutes under conditions of.
[0163]
　The obtained press sheet was subjected to Vicat softening temperature by the method described later (3mm thick using a pressed sheet) and steam resistance evaluation (using a press sheet of 3mm thick and 10mm thick). The results are shown in Table 1.
[0164]

　using the evaluation pellet mounted, Thermo Plastic Co. uniaxial extruder (screw diameter 20mmφ, L / D 28) coathanger type T-die to (lip shape 270 × 0.8 mm) to conditions of a die temperature of 270 ° C., a roll temperature of 70 ° C., subjected to molding at a winding speed 2.0 m / min, to obtain a film having a thickness of 50 [mu] m.
[0165]
　The obtained film, steam resistance evaluated by methods described below, to evaluate the high-temperature elastic modulus and tensile elongation. The results are shown in Table 1.
[0166]
　Hereinafter, the polymer, evaluation pellets are specifically described how to evaluate the press sheets and films. The evaluation results are shown in Table 1. In the table, "-" means that there is no data. Also in Figure 1, in Examples and Comparative Examples, showing the relationship between the heat of fusion and the melting point. The range of the solid line and on the solid line shown in FIG. 1 above satisfies "ΔHm ≧ 0.5 × Tm-76", is in the range of lower than the solid line does not meet the "ΔHm ≧ 0.5 × Tm-76" .
[0167]
[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) the content of constituent units derived from (comonomer) is the following apparatus and conditions, 13 was calculated from the C-NMR spectrum.
[0168]
　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.
[0169]
　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 It shows the total peak area of.
[0170]
[Meso diad fraction]
　4-methyl-1-pentene polymer meso die door iso tacticity (meso diad fraction) of the any two head-to-tail bonded 4-methyl-1-pentene units chain in the polymer chain when 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.
[0171]
　Iso diad tacticity (%) = [m / (m + r)] × 100
(wherein, m, r is the head represented by the following formula - attached at the tail 4-methyl-1-His pentene units shows the absorption intensity derived from a chain of methylene.)
　 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 a single pulse proton broadband decoupling pulse width 5.0μ sec (45 ° pulse ), the repetition time was 5.5 seconds, was measured 128ppm benzene -d6 as a reference value for the chemical shift.
[0172]
　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.
[0173]
　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%. [Mw / Mn, Mz / Mw , molecular weight of 1 × 10 6 ratio of the of the polymer or higher]
　weight average molecular weight (Mw), number average molecular weight (Mn) and Z average molecular weight (Mz) were measured by GPC. GPC measurement was carried out under the following conditions. The weight average molecular weight (Mw), number average molecular weight (Mn) and Z average molecular weight (Mz), a calibration curve using commercially available monodisperse standard polystyrene was determined based on the following conversion method.
[0174]
　(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
　in addition, the calculation of the general-purpose calibration, Mark-Houwink viscosity equation of using the coefficient. Each Mark-Houwink coefficients of PS, literature (J.Polym.Sci., Part A-2,8,1803 (1970)) was used values described.
[0175]
　Also, among the PS-converted GPC chart, the integrated area value of 1,000,000 or more components, the proportion of the entire integrated area charts, 1 × 10 6 was more component ratio.
[Melt flow rate (MFR) of]
　the melt flow rate (MFR) 260 ° C. in conformity with ASTM D1238, was measured under the conditions of 5kg load.
[0176]
[Decane-soluble component quantity]
　Each polymer 5g of n- decane 200mL was added and heated for 1 hour dissolution at 145 ° C.. It cooled to 23 ° C., and allowed to stand for 30 minutes. Thereafter, the precipitate (n- decane-insoluble portion) was filtered off. Put filtrate into approximately 3 volumes of acetone to precipitate a component that was dissolved in n- decane. The precipitate was separated by acetone Kararo and dried. It was measured mass of the precipitate. Even the filtrate side was concentrated to dryness The residue was observed. n- decane-soluble portion content was determined by the following equation.
[0177]
　n- decane soluble part amount (mass%) = [precipitation amount of substance / polymer mass] × 100
[melting point, heat of fusion]
　using Seiko Instruments Inc. DSC measurement apparatus (DSC220C), about 5mg to measurement aluminum pan packed samples were 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.
[0178]
Melt tension]
　For the measurement of the melt tension, was used Capirograph 1D is a device Toyo Seiki Seisakusho. After the sample was sufficiently melted was charged into a melting furnace set at 260 ° C. (diameter 9.55 mm) passes, at an extrusion rate of 15mm / min, L / D 8 / 2.095mm, the capillary is entrance angle 180 ° is allowed, 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.
[0179]
[Vicat Softening Temperature]
　The pressed sheet having a thickness of 3 mm, in compliance with ASTM D1525, using a testing machine manufactured by Yasuda Seiki Co., silicone oil, heating rate 50 ° C. per time, Vicat softening temperature at a test load 10N the test was carried out.
[0180]
[Steam resistance evaluation]
　The steam resistance evaluation was used Kusumoto Kasei Co., Ltd. HAST tester PLAMOUNT (PM252). 0.05 mm (50 [mu] m) thick film, 3 mm thickness and 10mm thick press sheet, 135 ° C., the appearance of the test piece after 2 cycles of operation for cooling to 23 ° C. After the 30 minute hold under the conditions of RH95% It was confirmed. × a case where whitening due voids or cracks occurred clearly the specimen, a case where whitening due voids or cracks in trace △, and the case where whitening due voids or cracks do not occur was evaluated as ○.
[0181]
[High-temperature elastic modulus E 'at 170 ° C.]
　with respect to the film, using a TA instruments, Inc. RSA-III, the measurement mode of the tensile, rise rate 4 ° C. per minute temperature, frequency 1 Hz, strain of 0.1% in conditions, measured from -20 ° C. to 250 ° C., was read the value of the storage modulus E 'at 170 ° C..
[0182]
Film tensile elongation]
　is a tensile properties Tensile elongation in compliance with JIS K678, as a test piece of the above film, using the Instron universal tensile tester 3380, measured at a pulling speed of 200 mm / min .
[0183]
[Table 1]

The scope of the claims
[Requested item 1]
　The content of the constitutional unit derived from 4-methyl-1-pentene is 90 to 100 mol%, at least one selected from ethylene and 3 to 20 carbon atoms 4-methyl-1-pentene other α- olefin of 0-10 mol% is the content of the constitutional unit derived from olefins, meet all the following requirements (a) ~ (e), 4- methyl-1-pentene polymer.
(A) 13 meso diad fraction as measured by C-NMR (m) is in the range 98 to 100%.
(B) measured by gel permeation chromatography (GPC), the ratio of the Z average molecular weight Mz and the weight average molecular weight Mw (Mz / Mw) is in the range of 2.5-20.
(C) were 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.
(D) conforms 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.
(E) 23 ° C. decane soluble part amount is more than 5.0 mass%.
[Requested item 2]
　Further 4-methyl-1-pentene polymer according to claim 1 which satisfies the following requirement (f).
(F) were measured by gel permeation chromatography (GPC), the molecular weight × 10 1 6 ratio of at least the polymer is not less than 15 mass%.
[Requested item 3]
　Further 4-methyl-1-pentene polymer according to claim 1 or 2 satisfies the following requirement (g).
(G) filling the is measured by differential scanning calorimetry (DSC) 4-methyl-1-pentene polymer heat of fusion and the melting point of the following requirements (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 200 ~ 260 ° C. It is in.
[Requested item 4]
　Resin composition comprising a 4-methyl-1-pentene polymer according to any one of claims 1 to 3.
[Requested item 5]
　Molded article comprising a resin composition according to 4-methyl-1-pentene polymer or claim 4 according to any one of claims 1 to 3.
[Requested item 6]
　The maximum thickness is at 100mm or less, and the minimum thickness is 0.001mm or more, the molded body according to claim 5.
[Requested item 7]
　An injection molded article or extrusion molded product, the molded body according to claim 5 or 6.
[Requested item 8]
　A film, molded article according to claim 5.
[Requested item 9]
　Medical is a molded body according to any claims 5-8, care, infant, for physicochemical experiments, food, lifestyle or instruments or containers for chemicals.