JP2017178982A - Film or sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film or sheet excellent in elongation, impact resistance and tear resistance and good in surface nature without deteriorating high rigidity of a 4-methyl-1-pentene-based polymer.SOLUTION: There is provided a film or a sheet containing a resin composition (A) containing 60 to 95 pts.mass of 4-methyl-1-pentene-based polymer (X) having a constitutional unit derived from 4-methyl-1-pentene of 90 to 100 mol%, a constitutional unit derived from ethylene and α-olefin having 3 to 20 carbon atoms of 0 to 10 mol% and satisfying (X-1) to (X-4) and 5 to 40 pts.mass of polyolefin (Y) having the melting point of 100°C or more, where total of (X) and (Y) is 100 pts.mass. (X-1) meso diad fraction is 98 to 100%. (X-2) MFR is 0.1 to 100 g/10 min. (X-3) 23°C decane soluble part amount is 5 mass% or less. (X-4) melting point is 200 to 260°C and melting heat amount is ΔHm≥0.5×Tm-76.SELECTED DRAWING: None

Description

  The present invention relates to a film or sheet containing a 4-methyl-1-pentene polymer having specific physical properties.

  4-methyl-1-pentene homopolymer or 4-methyl-1-pentene / α-olefin copolymer (hereinafter referred to as a homopolymer and a copolymer) containing 4-methyl-1-pentene as a main constituent monomer. Collectively called 4-methyl-1-pentene polymer) is excellent in heat resistance, releasability and chemical resistance, and is therefore widely used in various applications. For example, a film made of the polymer is used for an FPC release film, a composite material molding or a release film, taking advantage of features such as good release properties, or chemical resistance, water resistance, transparency, etc. Taking advantage of these features, they are used in laboratory instruments and mandrels for rubber hose manufacture.

  However, in general, the polymer is poor in elongation, impact resistance, and tear resistance, and, for example, there are restrictions on applicable applications as compared with polyethylene and polypropylene which are the same polyolefin. In addition, since stretchability is generally poor, for example, it is difficult to produce a stretched film or perform blow molding or vacuum molding compared to polyethylene and polypropylene, which are the same polyolefin, and there is a range that can be used. It was limited.

  On the other hand, various studies have been attempted for the purpose of improving the elongation, impact resistance, and tear resistance of the 4-methyl-1-pentene polymer.

For example, Patent Document 1 examines a wrap film made of a polymer in which 4-methyl-1-pentene and 1-hexene are copolymerized at a specific ratio.
Patent Document 2 discloses a hose made of a thermoplastic elastomer containing a 4-methyl-1-pentene polymer having excellent heat resistance, elongation and flexibility.
In Patent Document 3, a liquid hydrocarbon compound is blended with 4-methyl-1-pentene polymer resin.

In Patent Document 4, a high fluidity 4-methyl-1-pentene polymer resin and a low fluidity 4-methyl-1-pentene polymer resin are mixed under specific conditions.
In Patent Document 5, a 4-methyl-1-pentene polymer having specific physical properties, a 4-methyl-1-pentene / α-olefin copolymer, and a polyolefin are blended at a specific ratio.

JP 2001-172408 A International Publication No. 2002/081958 JP 58-191734 A JP 2003-292704 A International Publication No. 2013/099876 International Publication No. 2014/050817 Japanese Patent Laying-Open No. 2015-183141

  As described above, alloying technology is used for the purpose of improving the elongation, impact resistance, and tear resistance of the 4-methyl-1-pentene polymer. According to the study by the present inventors, 4-methyl- It has been found that the surface properties of a film or sheet may be lowered by alloying a specific polyolefin with a 1-pentene polymer. In applications where the appearance is important, the deterioration of surface properties can be a problem. This is presumed to be an effect due to poor dispersion of the blend. In addition, when a large amount of polyolefin is blended in order to obtain the desired toughness improving effect, the rigidity that is the original characteristic of the 4-methyl-1-pentene polymer may be impaired.

  An object of the present invention is to solve the above-described problems of the prior art. That is, an object of the present invention is to provide a film or sheet that is excellent in elongation, impact resistance, tear resistance, and surface properties without impairing the high rigidity characteristics of the 4-methyl-1-pentene polymer. Is to provide.

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problem can be solved by using a 4-methyl-1-pentene polymer having a specific composition and specific characteristics, and has completed the present invention.

The present invention relates to the following [1] to [4].
[1] The content of structural units derived from 4-methyl-1-pentene is 90 to 100 mol%, and is selected from ethylene and α-olefins other than 4-methyl-1-pentene having 3 to 20 carbon atoms. The content of the structural unit derived from at least one olefin is 0 to 10 mol%, and satisfies the following requirements (X-1) to (X-4): 4-methyl-1-pentene polymer (X) 60 -95 parts by mass and polyolefin (Y) 5-40 parts by mass (however, (X) and different from the 4-methyl-1-pentene polymer (X) and satisfying the following requirement (Y-1)) A film or sheet comprising a resin composition (A) comprising (Y) a total of 100 parts by mass).
(X-1) Meso-dyad fraction (m) measured by ¹³ C-NMR is in the range of 98 to 100%.
(X-2) Melt flow rate (MFR) measured in accordance with ASTM D1238 under a load condition of 260 ° C. and 5 kg is in the range of 0.1 to 100 g / 10 min.
(X-3) 23 degreeC decane soluble part amount is 5 mass% or less.
(X-4) The heat of fusion and melting point measured by differential scanning calorimetry (DSC) satisfy the following requirements (i) and (ii).
(I) The following formula (1) is established.
ΔHm ≧ 0.5 × Tm−76 (1)
(In the formula (1), the heat of fusion is ΔHmJ / g, and the melting point is Tm ° C.)
(Ii) Melting | fusing point exists in the range of 200-260 degreeC.
(Y-1) The melting point measured by differential scanning calorimetry (DSC) is 100 ° C. or higher.
[2] The film or sheet according to [1], wherein the polyolefin (Y) is polypropylene.
[3] The film or sheet according to [1] or [2], wherein the polypropylene (Y) satisfies the following requirements (Y-2) and (Y-3).
(Y-2) Content of the structural unit derived from propylene is 90 mol% or more.
(Y-3) MFR (230 ° C., 2.16 kg load) is in the range of 0.1 to 100 g / 10 min.
[4] The film or sheet according to any one of [1] to [3], wherein the 4-methyl-1-pentene polymer (X) satisfies the following requirements (X-5) and (X-6): .
(X-5) The ratio (Mz / Mw) of the Z average molecular weight Mz and the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is in the range of 2.5-20.
(X-6) The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) is in the range of 3.6-30.

  When the 4-methyl-1-pentene polymer and the resin composition of the present invention are used, elongation, impact resistance, and tear resistance are maintained without impairing the high rigidity characteristics of the 4-methyl-1-pentene polymer. It is possible to provide a film or sheet having excellent surface properties and excellent surface properties.

  Hereinafter, the film or sheet according to the present invention will be described in detail. The film or sheet of the present invention contains a resin composition (A).

<Resin composition (A)>
Resin composition (A) contains 4-methyl-1-pentene polymer (X) and polyolefin (Y), and the mass ratio is 100 parts by mass of the total of (X) and (Y). Sometimes, it contains 60 to 95 parts by mass of 4-methyl-1-pentene polymer (X) and 5 to 40 parts by mass of polyolefin (Y).

<4-Methyl-1-pentene polymer (X)>
The 4-methyl-1-pentene polymer (X) has a content of constituent units derived from 4-methyl-1-pentene with respect to all constituent units contained in the polymer (X) of 90 to 100 mol%, The content of structural units derived from at least one olefin selected from ethylene and α-olefins other than 4-methyl-1-pentene having 3 to 20 carbon atoms (hereinafter also referred to as comonomer) is 0 to 10 mol%. Yes, the following requirements (X-1) to (X-4) are satisfied, and preferably one or more of the following requirements (X-5) and (X-6) are satisfied. In addition, when the 4-methyl-1-pentene polymer (X) is a blended product of a plurality of 4-methyl-1-pentene polymers, the above-mentioned definition is that the blended product is a requirement (X-1 ) To (X-4), preferably one or more of the requirements (X-5) and (X-6).

  The 4-methyl-1-pentene polymer (X) is, for example, a homopolymer of 4-methyl-1-pentene (that is, the content of structural units derived from 4-methyl-1-pentene is 100 mol%. Some polymers) and copolymers of 4-methyl-1-pentene with other olefins.

  Here, from the viewpoint of transparency and heat resistance, a configuration derived from 4-methyl-1-pentene for all the structural units contained in the polymer (X) in the 4-methyl-1-pentene polymer (X). The content of the unit is preferably 92 to 100 mol%, more preferably 95 to 100 mol%, and is selected from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene). The total content of structural units derived from at least one olefin is preferably 0 to 8 mol%, more preferably 0 to 5 mol%.

  When 4-methyl-1-pentene-based polymer (X) is a copolymer, specifically, ethylene that is copolymerized with 4-methyl-1-pentene and α-olefin having 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, Examples include 1-hexadecene, 1-octadecene, and 1-eicocene. Of these, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene, and these α-olefins may be used alone or in combination of two or more.

  In the present invention, a structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (X), and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl- The amount of the structural unit derived from at least one olefin selected from (excluding 1-pentene) is 4-methyl-1-pentene added during the polymerization reaction, and ethylene and α-carbon having 3 to 20 carbon atoms. It can be adjusted by the amount of at least one olefin selected from olefins (excluding 4-methyl-1-pentene).

Hereinafter, each requirement that the 4-methyl-1-pentene polymer (X) satisfies will be described.
(Requirement (X-1))
^The mesodyad fraction (m) measured by ¹³ C-NMR is in the range of 98 to 100%, preferably in the range of 98.5 to 100%.

  When the meso-dyad fraction (m) of the 4-methyl-1-pentene polymer (X) is not less than the lower limit, a molded product containing the 4-methyl-1-pentene polymer (X) is sufficient. It will be equipped with performance such as heat resistance and rigidity.

  In the present invention, the mesodyad fraction (m) of the 4-methyl-1-pentene polymer (X) can be adjusted according to the type of the olefin polymerization catalyst described later.

(Requirement (X-2))
The 4-methyl-1-pentene polymer (X) has a melt flow rate (MFR) of 0.1 to 100 g / 10 min measured under conditions of 260 ° C. and 5 kg load according to ASTM D1238, preferably It is 1-100 g / 10min, More preferably, it is 2-100 g / 10min, More preferably, it is 5-80 g / 10min.

  When the MFR of the 4-methyl-1-pentene polymer (X) is in the above range, it is preferable from the viewpoint of resin fluidity during the production of a molded body.

  In the present invention, the method for adjusting the MFR of the 4-methyl-1-pentene polymer (X) includes adjusting the amount of hydrogen in the reactor during the polymerization reaction, or having different MFRs during or after the polymerization. There are methods of blending different types of polymers.

(Requirement (X-3))
The 4-methyl-1-pentene polymer (X) has a 23 ° C. decane soluble part amount of 5.0% by mass or less, preferably 3.0% by mass or less, more preferably 1.0% by mass or less. It is.

  In the present invention, the 23 ° C. decane-soluble part amount is 1 to 145 ° C. when 4-methyl-1-pentene polymer (X) is added to n-decane as described in detail in Examples below. The ratio of the weight of the polymer (X) dissolved in the n-decane solution to the weight of the added polymer (X) when the n-decane solution was cooled to 23 ° C. after being heated and dissolved for a time. Show.

  The small amount of the 23 ° C. decane soluble part of the 4-methyl-1-pentene polymer (X) indicates that the amount of the low molecular weight polymer contained in the polymer (X) is small. The low molecular weight which becomes a contaminating component from the molded object obtained from the resin composition containing the said polymer because the 23 degreeC decane soluble part amount of 4-methyl- 1-pentene type polymer (X) exists in the said range. Since it becomes possible to suppress the outflow of components, it can be suitably used for applications such as films that require high purity.

  In the present invention, the amount of the 23 ° C. decane soluble part of the 4-methyl-1-pentene polymer (X) can be adjusted by the type of the olefin polymerization catalyst described later.

(Requirement (X-4))
The heat of fusion and melting point of the 4-methyl-1-pentene polymer (X) measured by differential scanning calorimetry (DSC) satisfy the following requirements (i) and (ii).
(I) The following formula (1) is established.
ΔHm ≧ 0.5 × Tm−76 (1)
(In the formula (1), the heat of fusion is ΔHmJ / g, and the melting point is Tm ° C.)
(Ii) Melting | fusing point exists in the range of 200-260 degreeC.

  The heat of fusion (ΔHmJ / g) measured by differential scanning calorimetry (DSC) (temperature increase rate: 10 ° C./min) in the above requirement (i) is preferably 5 to 80 J / g, more preferably 10 ~ 60 J / g. The melting point (Tm ° C.) measured by differential scanning calorimetry (DSC) (temperature increase rate: 10 ° C./min) in the above requirement (ii) is preferably 200 to 250 ° C., more preferably 205 to It is 250 degreeC, More preferably, it is 210-245 degreeC.

  The requirement (i) indicates that the 4-methyl-1-pentene polymer (X) according to the present invention has a high heat of fusion. Specifically, the 4-methyl-1-pentene polymer (X) according to the present invention has a feature that the heat of fusion with respect to the melting point is large, that is, the crystallinity is high.

  This requirement is disclosed in detail in Patent Document 6, and similarly disclosed in Patent Document 7. The 4-methyl-1-pentene polymer disclosed in Patent Documents 6 and 7 also satisfies this requirement. Production Example 1 [Polymer A-1] described later satisfies this requirement, and Production Example 2 [Polymer A-2] does not satisfy this requirement.

  In the present invention, the heat of fusion of the 4-methyl-1-pentene polymer (X) can be adjusted within the above specified range by using an olefin polymerization catalyst described later. Moreover, melting | fusing point can be adjusted by adjusting the ratio of the structural unit of 4-methyl-1- pentene in the said requirement (a) simultaneously with using the said catalyst for olefin polymerization.

(Requirement (X-5))
The ratio (Mz / Mw) of the Z average molecular weight Mz and the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is in the range of 2.5 to 20, preferably 2.5 to 15, more preferably Is in the range of 2.7-15, more preferably 2.8-15. When the ratio (Mz / Mw) is in the above range, a molded article such as a film containing the 4-methyl-1-pentene polymer (X) is excellent in elongation, impact resistance, and tear resistance. Further, the ratio (Mz / Mw) being in the above range suggests that a considerable amount of a polymer having a large molecular weight is contained in the 4-methyl-1-pentene polymer (X). The method for adjusting the ratio (Mz / Mw) to the above range will be described later in detail.

(Requirement (X-6))
The ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn measured by gel permeation chromatography (GPC) is in the range of 3.6 to 30, preferably 3.6 to 25, more preferably. Is in the range of 3.8 to 25, more preferably 4.0 to 25. When the ratio (Mw / Mn) is in the above range, a molded article such as a film containing the 4-methyl-1-pentene polymer (X) is excellent in elongation, impact resistance, and tear resistance. Further, the ratio (Mw / Mn) being in the above range suggests that there is a considerable amount of a polymer having a large molecular weight in the 4-methyl-1-pentene polymer (X). The method for adjusting the ratio (Mw / Mn) of the 4-methyl-1-pentene polymer (X) to the above range will be described in detail later.

<Method for producing 4-methyl-1-pentene polymer (X)>
The 4-methyl-1-pentene polymer (X) is obtained by polymerizing 4-methyl-1-pentene in the presence of an olefin polymerization catalyst described later, or 4-methyl-1-pentene and ethylene and carbon. It can be obtained by copolymerizing with at least one olefin selected from α-olefins having 3 to 20 atoms (excluding 4-methyl-1-pentene).

[1-1] Olefin Polymerization Catalyst As an olefin polymerization catalyst,
A bridged metallocene compound (A);
(B-1) Organometallic compound (B-2) Organoaluminum oxy compound (B-3) (A) reacts with at least one compound (B) selected from compounds that form ion pairs. The catalyst comprising is preferred.

<Bridged metallocene compound (A)>
The bridged metallocene compound (A) is preferably a compound represented by the general formula [A1], and more preferably a compound represented by the general formula [A2].

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

In the formula [A2], R ¹ is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R ^{2 to} R ¹⁰ are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group. Each may be the same or different, and each substituent may be bonded to each other to form a ring. M is a Group 4 transition metal in the periodic table, and Q is a neutral atom capable of coordinating with a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and a lone electron pair. The ligands are selected from the same or different combinations, and j is an integer of 1 to 4.

  Among the bridged metallocene compounds represented by the general formula [A2], the bridged metallocene compounds represented by the general formula [A3] are particularly preferable from the viewpoint of obtaining polymerization characteristics, availability, and a butene-based polymer that satisfies the above requirements. .

In the formula [A3], R ^1b is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R ^{2b to} R ^12b are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group. Each may be the same or different, and each substituent may be bonded to each other to form a ring. M is a Group 4 transition metal in the periodic table, n is an integer of 1 to 3, Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and The neutral ligands that can be coordinated by a lone electron pair are selected from the same or different combinations, and j is an integer of 1 to 4.

<R ¹ to R ¹⁰ , R ^1b to R ^12b >
Examples of the hydrocarbon group in R ¹ to R ¹⁰ and R ^1b to R ^12b include a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a saturated hydrocarbon group. And a group formed by substituting one or two or more hydrogen atoms possessed by a cyclic unsaturated hydrocarbon group. Carbon number of a hydrocarbon group is 1-20 normally, Preferably it is 1-15, More preferably, it is 1-10.

  Examples of the linear hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. And linear alkyl groups such as n-decanyl group; linear alkenyl groups such as allyl group.

  Examples of the branched hydrocarbon group include isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1 Examples thereof include branched alkyl groups such as -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group.

  Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and methylcyclohexyl group; and polycyclic groups such as norbornyl group, adamantyl group, and methyladamantyl group. It is done.

  Examples of the cyclic unsaturated hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group; a cycloalkenyl group such as a cyclohexenyl group; and 5-bicyclo [2.2. 1] Polycyclic unsaturated alicyclic groups such as a hepta-2-enyl group.

  Examples of the group formed by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include a benzyl group, a cumyl group, a 1,1-diphenylethyl group, and a triphenylmethyl group. And a group formed by substituting one or two or more hydrogen atoms of the alkyl group with an aryl group.

The silicon-containing group in R ^12b from R ¹ from R ¹⁰ and R ^1b, for example, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, the formula -SiR _3, such as a triphenylsilyl group (wherein And a plurality of R's are each independently an alkyl group having 1 to 15 carbon atoms or a phenyl group.).

Examples of the halogen-containing hydrocarbon group in R ¹ to R ¹⁰ and R ^1b to R ^12b are formed by substituting one or more hydrogen atoms of the hydrocarbon group such as a trifluoromethyl group with a halogen atom. Groups.

Examples of the halogen atom in R ² to R ¹⁰ and R ^2b to R ^12b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Of the substituents R ² to R ¹⁰ and R ^2b to R ^12b , 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 ) may be bonded to each other to form a ring, and there are two or more ring formations in the molecule. May be.

  In the present invention, examples of the ring (spiro ring, additional ring) formed by bonding two substituents to each other include an alicyclic ring and an aromatic ring. Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, and a cyclopentene ring, and a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring are preferable. Such a ring structure may further have a substituent such as an alkyl group on the ring.

R ^1b is preferably a hydrocarbon group from the viewpoint of stereoregularity, more preferably a hydrocarbon group having 1 to 20 carbon atoms, still more preferably not an aryl group, and a linear hydrocarbon. Group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group is particularly preferable, and a substituent having a free valence (carbon bonded to a cyclopentadienyl ring) being a tertiary carbon is particularly preferable. preferable.

Specific examples of R ^1b include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group. Is a substituent in which the carbon having a free valence is a tertiary carbon, such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, or a 1-adamantyl group, particularly preferably a tert-butyl group, 1- An adamantyl group;

In the general formula [A3], the fluorene ring moiety is not particularly limited as long as it is a structure obtained from a known fluorene derivative, but R ^4b and R ^5b are preferably hydrogen atoms from the viewpoint of stereoregularity and molecular weight.

R ^2b , R ^3b , R ^6b and R ^7b are preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrocarbon group, and still more preferably a hydrocarbon group having 1 to 20 carbon atoms. R ^2b and R ^3b may be bonded to each other to form a ring, and R ^6b and R ^7b may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl 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-1'H, 8'H-dicyclopenta [B, h] fluorenyl group is exemplified, and 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro- is particularly preferred. 1H-dibenzo [b, h] fluorenyl group.
R ^8b is preferably a hydrogen atom.

R ^9b is more preferably a hydrocarbon group, and R ^9b is more preferably an alkyl group having 2 or more carbon atoms such as a linear alkyl group or a branched alkyl group, a cycloalkyl group, or a cycloalkenyl group, R ^9b is particularly preferably an alkyl group having 2 or more carbon atoms. From the viewpoint of synthesis, R ^10b and R ^11b are also preferably hydrogen atoms.

Alternatively, when n = 1, R ^9b and R ^10b are more preferably bonded to each other to form a ring, and the ring is particularly preferably a 6-membered ring such as a cyclohexane ring. In this case, R ^11b is preferably a hydrogen atom.
R ^12b is preferably a hydrocarbon group, and particularly preferably an alkyl group.

<About M, Q, n, and j>
M is a Group 4 transition metal of the periodic table, for example, Ti, Zr or Hf, preferably Zr or Hf, and particularly preferably Zr.

Q represents a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair.
Examples of the halogen atom for Q include fluorine, chlorine, bromine and iodine.

  As a hydrocarbon group in Q, a C1-C10 alkyl group and a C3-C10 cycloalkyl group are preferable. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1 , 1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1, Examples include a 1,3-trimethylbutyl group and a neopentyl group; examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclohexylmethyl group, a cyclohexyl group, and a 1-methyl-1-cyclohexyl group. More preferably, the hydrocarbon group has 5 or less carbon atoms.

Neutral conjugated or non-conjugated dienes having 10 or less carbon atoms include s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4- Diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1, 3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s- cis - or s- trans eta ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

  Examples of the anionic ligand include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.

Neutral ligands that can be coordinated by lone electron pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-dimethoxy Examples are ethers such as ethane.
A preferred embodiment of Q is a halogen atom or an alkyl group having 1 to 5 carbon atoms.

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

The preferred embodiments of the configuration of the bridged metallocene compound represented by the general formula [A2] or [A3], that is, R ^{1 to} R ¹⁰ , R ^{1b to} R ^12b , M, n, Q, and j have been described above. In the present invention, any combination of the preferred embodiments is also a preferred embodiment. Such a bridged metallocene compound can be suitably used to obtain the butene polymer of the present invention having the above physical properties.

  Examples of the bridged metallocene compound represented by the general formula [A3] include (8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5, 6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride or (8- (2,3,6,7-tetramethylfluorene) -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 above-mentioned octamethylfluorene is 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b , h] Fluorene.

<Compound (B)>
The catalyst for olefin polymerization is
(B-1) Organometallic compound (B-2) Organoaluminum oxy compound (B-3) At least one compound selected from compounds that react with (A) to form an ion pair (hereinafter referred to as “compound (B)” Also called.)
It is preferable to contain.

  Specific examples of the compound (B), the carrier (C) and the organic compound component (D) described later are as disclosed in Patent Documents 3 and 4 or International Publication No. 2014-123212. For the carrier (C), examples disclosed in International Publication No. 2010-055652, International Publication No. 2011-142400, International Publication No. 2013-146337, and Japanese Patent Application Laid-Open No. 2015-74645 can be applied.

<Carrier (C)>
More preferably, the olefin polymerization catalyst further contains a carrier (C).
Examples of the carrier (C) include inorganic or organic compounds and granular or fine particle solids. The transition metal compound (A) is preferably used in a form supported on the carrier (C).

<Organic compound component (D)>
The olefin polymerization catalyst of the present invention may further contain (D) an organic compound component, if necessary. The organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of the organic compound (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

<Method of adjusting ratio (Mz / Mw) and ratio (Mw / Mn)>
The ratio (Mz / Mw) and ratio (Mw / Mn) of 4-methyl-1-pentene-based polymer (X) is a multi-stage polymerization method such as single-stage or two-stage polymerization. Adjustment is possible by blending during or after polymerization.

  In Examples 1 and 2 of the present invention, the ratio (Mz / Mw) and (Mz / Mw) were determined by dividing hydrogen into “initial stage of polymerization” and “in the middle of polymer production” while being single-stage polymerization. Mw / Mn) is adjusted to an arbitrary value, and adjustment is also possible by such a method. More specifically, a high molecular weight polymer is polymerized by reducing the amount of hydrogen introduced at the initial stage of polymerization, and a relatively low molecular weight polymer is polymerized by feeding a larger amount of hydrogen at a stage where the polymerization has progressed to some extent. The ratio (Mz / Mw) and (Mw / Mn) of the finally obtained polymer can be adjusted.

<Resin composition containing 4-methyl-1-pentene polymer (X)>
The resin composition containing 4-methyl-1-pentene polymer (X) in the present invention comprises the 4-methyl-1-pentene polymer (X) as an essential component, and other moldings according to the present invention. Various components are included depending on the purpose of the body.

[Various components other than 4-methyl-1-pentene polymer (X)]
The resin composition containing the 4-methyl-1-pentene polymer (X) can optionally contain other resins, polymers, additives for resins, and the like within the range that does not impair the effects of the present invention. Can be contained.

  As other resins or polymers to be added, the following thermoplastic resins (E) can be widely used. It is preferable that the addition amount of these resin or polymer is 0.1-30 mass% with respect to the total mass of a resin composition.

  The thermoplastic resin (E) is not particularly limited as long as it is different from the 4-methyl-1-pentene polymer (X) according to the present invention, and examples thereof include the following resins.

Thermoplastic polyolefin resin, for example, low density, medium density, high density polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1-pentene, poly 3 -Methyl-1-pentene, poly-3-methyl-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer, 4-methyl-1 A pentene / α-olefin copolymer, a cyclic olefin copolymer, a chlorinated polyolefin, and a modified polyolefin resin obtained by modifying these olefin resins;
Thermoplastic polyamide resin, for example, aliphatic polyamide (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612),
Thermoplastic polyester resin; for example, polyethylene terephthalate, polybutylene terephthalate, polyester elastomer;
Thermoplastic vinyl aromatic resins such as polystyrene, ABS resin, AS resin, styrene elastomer (styrene / butadiene / styrene block polymer, styrene / isoprene / styrene block polymer, styrene / isobutylene / styrene block polymer, hydrogenated as described above) object);
Thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; ethylene / vinyl acetate copolymer; ethylene / methacrylic acid acrylate copolymer; ionomer; ethylene / vinyl alcohol copolymer; polyvinyl alcohol; Polyacetal; Polyphenylene oxide; Polyphenylene sulfide polyimide; Polyarylate; Polysulfone; Polyethersulfone; Rosin resin; Terpene resin and petroleum resin;
Copolymer rubber, for example, ethylene / α-olefin / diene copolymer, propylene / α-olefin / diene copolymer, 1-butene / α-olefin / diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene Examples thereof include rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, and silicone rubber.

  Examples of polypropylene include isotactic polypropylene and syndiotactic polypropylene. The isotactic polypropylene may be a homopolypropylene, a propylene / α-olefin having 2 to 20 carbon atoms (excluding propylene) random copolymer, or a propylene block copolymer.

  Poly-4-methyl-1-pentene and 4-methyl-1-pentene / α-olefin copolymer are polymers different from 4-methyl-1-pentene polymer (X), and 4-methyl- 1-pentene homopolymer or 4-methyl-1-pentene / α-olefin random copolymer. In the case of 4-methyl-1-pentene / α-olefin random copolymer, the α-olefin copolymerized with 4-methyl-1-pentene includes ethylene, propylene, 1-butene, 1-hexene and 1-octene. , 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc., and an α-olefin having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms. These can be used alone or in combination of two or more. The melt flow rate (MFR; ASTM D1238, 260 ° C., 5.0 kg load) is preferably 0.1 to 200 g / 10 minutes, more preferably 1 to 150 g / 10 minutes. A commercially available product can be used as poly-4-methyl-1-pentene, and examples thereof include TPX (trade name) manufactured by Mitsui Chemicals. Poly 4-methyl-1-pentene from other manufacturers can be preferably used as long as the above requirements are satisfied.

  As the polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, and high pressure method low density polyethylene, which are produced by a conventionally known method, can be used.

  Examples of the polybutene include a homopolymer of 1-butene or a copolymer of 1-butene and an olefin excluding 1-butene. Examples of the olefin copolymerized with polybutene include the α-olefin mentioned as the α-olefin copolymerized with 4-methyl-1-pentene. These olefins are used alone or in combination of two or more. It is done. Examples of the copolymer include 1-butene / ethylene random copolymer, 1-butene / propylene random copolymer, 1-butene / methylpentene copolymer, 1-butene / methylbutene copolymer, 1-butene / Examples include propylene / ethylene copolymers. In such a copolymer, from the viewpoint of heat resistance, the content of the structural unit derived from 1-butene is preferably 50 mol% or more, more preferably 70 mol% or more, and 85% or more. It is particularly preferred.

  The modified polyolefin resin can be obtained by graft-modifying the above-described polyolefin resin with an ethylenically unsaturated bond-containing monomer using an organic peroxide. Examples of functional groups possessed by the modified polyolefin include halogen atoms, carboxyl groups, acid anhydride groups, epoxy groups, hydroxyl groups, amino groups, amide groups, imide groups, ester groups, alkoxysilane groups, acid halide groups, and nitrile groups. Is mentioned.

  Examples of rosin resins include natural rosin, polymerized rosin, modified rosin and rosin derivatives modified with maleic acid, fumaric acid, (meth) acrylic acid, and the like. Examples of the rosin derivative include the above-mentioned natural rosin, polymerized rosin or esterified product of modified rosin, phenol-modified product and esterified product thereof. Furthermore, these hydrogenated substances can also be mentioned.

  Examples of the terpene resin include resins composed of α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, etc., and α-pinene, β-pinene, limonene, dipentene, An aromatic modified terpene resin obtained by polymerizing an aromatic monomer may also be used. Moreover, these hydrogenated substances can also be mentioned.

  Examples of the petroleum resin include an aliphatic petroleum resin whose main raw material is a C5 fraction of tar naphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and a copolymer petroleum resin thereof. That is, C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) And a co-polymer of C9 fraction), a coumarone indene resin containing styrenes, indenes, coumarone, other dicyclopentadiene, etc. of the tar naphtha fraction, p-tert-butylphenol and Examples thereof include alkylphenol resins typified by condensates of acetylene, xylene resins obtained by reacting o-xylene, p-xylene or m-xylene with formalin.

  One or more resins selected from the group consisting of rosin resins, terpene resins, and petroleum resins are preferably hydrogenated derivatives because they are excellent in weather resistance and discoloration resistance. The softening point of the resin by the ring and ball method is preferably in the range of 40 to 180 ° C. The number average molecular weight (Mn) molecular weight measured by GPC of the resin is preferably in the range of about 100 to 10,000. Commercially available products can be used for the rosin resin, terpene resin and petroleum resin.

  Among these thermoplastic resins (E), preferred are low density, medium density, high density polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4- Methyl-1-pentene, poly-3-methyl-1-pentene, poly-3-methyl-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer Polymers, styrene elastomers, vinyl acetate copolymers, ethylene / methacrylic acid acrylate copolymers, ionomers, fluorine resins, rosin resins, terpene resins and petroleum resins, more preferred are improved heat resistance, Polyethylene, isotactic polypropylene, Shinji in terms of improved low temperature resistance and flexibility Tactic polypropylene, poly 1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer, vinyl acetate copolymer, styrene elastomer, rosin Resins, terpene resins and petroleum resins.

  The thermoplastic resin (E) is preferably poly-3-methyl-1-pentene, poly-3-methyl-1-butene, etc., and these are 4-methyl-1-pentene polymers (X ) Contributes to improving the rigidity of the resulting film and the like.

  As a thermoplastic resin (E), 1 type can also be used independently from the said thermoplastic resin, and it can also be used in combination of 2 or more type.

  Examples of additives for resins include nucleating agents, anti-blocking agents, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, Antistatic agent, weathering stabilizer, heat resistance stabilizer, anti-slip agent, foaming agent, crystallization aid, antifogging agent, (transparent) nucleating agent, anti-aging agent, hydrochloric acid absorbent, impact modifier, crosslinking agent, Examples include a co-crosslinking agent, a crosslinking aid, a pressure-sensitive adhesive, a softening agent, and a processing aid. These additives can be used singly or in appropriate combination of two or more.

  As the nucleating agent, a known nucleating agent may be used to further improve the moldability of the 4-methyl-1-pentene polymer (X), that is, to increase the crystallization temperature and increase the crystallization speed. Is possible. Specifically, dibenzylidene sorbitol nucleating agent, phosphate ester nucleating agent, rosin nucleating agent, benzoic acid metal salt nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di-t -Butylphenyl) sodium phosphate, pimelic acid and its salt, 2,6-naphthalene dicarboxylic acid dicyclohexylamide and the like. Although the compounding quantity of a nucleating agent is not specifically limited, Preferably it is 0.1-1 mass part with respect to 100 mass parts of 4-methyl-1- pentene-type polymer (X). The nucleating agent can be appropriately added during polymerization, after polymerization, or at the time of molding processing.

  As the anti-blocking agent, known anti-blocking agents can be used. Specifically, fine powder silica, fine powder aluminum oxide, fine powder clay, powdered or liquid silicon resin, tetrafluoroethylene resin, fine powder cross-linked resin, for example, cross-linked acrylic, methacrylic resin powder, etc. it can. Of these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferred.

  Examples of the pigment include inorganic contents (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of the dye include azo series, anthraquinone series, and triphenylmethane series. The addition amount of these pigments and dyes is not particularly limited, but is generally 5% by mass or less, preferably 0.1 to 3% in total with respect to the total mass of the 4-methyl-1-pentene polymer resin composition. % By mass.

  Fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal oxide ( Iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate, etc.) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powder, mica, glass flakes and the like. These fillers may be used alone or in combination of two or more.

  Examples of the lubricant include wax (such as carnauba wax), higher fatty acid (such as stearic acid), higher alcohol (such as stearyl alcohol), and higher fatty acid amide (such as stearic acid amide).

  Examples of plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetylricinoleate), aliphatic dialcolic acid esters (such as adipic acid-propylene glycol polyester), and aliphatic tricarboxylic acids. Examples include esters (such as triethyl citrate), phosphoric acid triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

  Examples of mold release agents include lower (C1-4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters (such as hardened castor oil) of fatty acids (C4-30), glycol esters of fatty acids, liquid paraffin, etc. Is mentioned.

  A known antioxidant can be used as the antioxidant. Specifically, phenolic (2,6-di-t-butyl-4-methylphenol and the like), polycyclic phenolic (2,2′-methylenebis (4-methyl-6-t-butylphenol and the like), phosphorus System (tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonate, etc.), sulfur system (dilauryl thiodipropionate, etc.), amine system (N, N-diisopropyl-p-) Phenylenediamine, etc.), lactone-based antioxidants, and the like.

  Examples of flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). Can be mentioned.

  Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylic acid, and acrylate.

  Antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, organic iodine, and the like.

  Surfactants can include nonionic, anionic, cationic or amphoteric surfactants. Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, fatty acid esters of polyethylene oxide and glycerin. Polyanhydric alcohol type nonionic surfactants such as fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, etc. For example, sulfate salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates, 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 amphoteric surfactants include amino acid-type double-sided surfactants such as higher alkylaminopropionates, betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyl hydroxyethylbetaine.

  Examples of the antistatic agent include the above surfactants, fatty acid esters, and polymer antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymer antistatic agents include polyether ester amides.

  The addition amount of various additives such as the above fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, and the like impairs the purpose of the present invention. Although not particularly limited depending on the use within the range, it is 0.1 to 30% by mass with respect to the total mass of the resin composition containing 4-methyl-1-pentene polymer (X). It is preferable.

<Polyolefin (Y)>
The polyolefin (Y) is different from the 4-methyl-1-pentene polymer (X) according to the present invention, and one or two selected from ethylene and an α-olefin having 3 to 20 carbon atoms. It is a polymer of more than one kind of olefin, for example, an olefin homopolymer or a binary or more copolymer. For example, in the case of a binary copolymer, the constituent unit of each olefin may be 50 to 99% by mass on the one hand and 1 to 50% by weight on the other, but is not particularly limited. In the case of a ternary or higher copolymer, the composition ratio of each olefin is arbitrarily determined.

Examples of ethylene and linear α-olefins having 3 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene and 1-dodecene. , 1-tetradecene, 1-hexadecene, 1-octadecene, α-olefin such as 1-eicosene.
Examples of the branched α-olefin having 4 to 20 carbon atoms include isobutene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, and 4-methyl-1- Α-olefins such as pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene Is mentioned.
The polyolefin (Y) satisfies the following requirement (Y-1), and preferably further satisfies one or more of the following requirements (Y-2) and (Y-3).

(Requirement (Y-1))
The melting point measured by differential scanning calorimetry (DSC) is 100 ° C. or higher. When the melting point of the polyolefin (Y) is within the above range, the polyolefin (Y) bleed out from the obtained film or sheet is preferably reduced.

(Requirement (Y-2))
Content of the structural unit derived from propylene is 90 mol% or more. That is, the polyolefin (Y) is preferably polypropylene. Since polypropylene is highly miscible with 4-methyl-1-pentene as compared with other polyolefins, it is preferably in the above range having a high propylene content. Polypropylene may be a homopolymer of propylene (homopolymer), or a copolymer of propylene and other monomers (copolymer), and the copolymer may be a random copolymer or block copolymer. Examples are polymers. Moreover, there is no restriction | limiting in particular in the stereoregularity, An isotactic polymer, a syndiotactic polymer, a mixture thereof, etc. can be mentioned.

(Requirement (Y-3))
MFR (230 degreeC, 2.16kg load) exists in the range of 0.1-100 g / 10min.

  When the MFR of the polyolefin (Y) is in the above range, the fluidity of the resin composition (A) is suitable for film or sheet molding, and is preferable. If it is larger than this, the film will be drawn down and the film thickness will be non-uniform.

<Production method of polyolefin (Y)>
The manufacturing method of polyolefin Y is not specifically limited, It can manufacture by a conventionally well-known method. For example, a commercially available product may be used, and Prime Polypro (trademark) manufactured by Prime Polymer may be used.

<Method for Producing Resin Composition (A)>
Although the manufacturing method of a resin composition (A) is not specifically limited, For example, after mixing 4-methyl- 1-pentene polymer (X), polyolefin (Y), and another component by the above-mentioned addition ratio, Obtained by melt-kneading.

  The method of melt kneading is not particularly limited, and can be performed using a melt kneading apparatus such as a commercially available extruder.

  For example, the cylinder temperature of the kneading part in the kneader is usually 250 to 320 ° C, preferably 260 to 300 ° C. When the cylinder temperature is lower than 250 ° C., kneading becomes insufficient due to insufficient melting, and it is difficult to improve the physical properties of the resin composition. On the other hand, when the temperature is higher than 320 ° C., thermal decomposition of the 4-methyl-1-pentene polymer (X) may occur. The kneading time is usually 0.1 to 30 minutes, particularly preferably 0.5 to 5 minutes. If the kneading time is less than 0.1 minutes, sufficient melt-kneading is not performed, and if the kneading time exceeds 30 minutes, the thermal decomposition of 4-methyl-1-pentene polymer (X) or polyolefin (Y) May happen.

<Film or sheet>
A film or a sheet is obtained by molding the resin composition (A).
(1) Molding method As the molding method of the resin composition, various known molding methods can be applied. For example, various methods such as a casting mold molding method, a calendar molding method, press molding, stamping molding, inflation molding, roll molding and the like. A molding method can be mentioned. By these molding methods, it can be processed into a desired film or sheet. The molding conditions are the same as those of a conventionally known 4-methyl-1-pentene polymer.
(2) Thickness The thickness of the film or sheet is preferably 0.1 μm to 10 mm. If it is thinner than this, handling such as conveyance of the molded article becomes difficult. If it is thicker than this, there will be no bending as a film or sheet, and cracking will easily occur when folded.
(3) Application The molded article of the present invention can be used without limitation for applications in which a conventional 4-methyl-1-pentene polymer can be used.

  The elongation of the film is required as a characteristic at the time of film formation, but there is no restriction on the use of the film. Examples of film applications include foods, meat, processed fish, vegetables, fruits, fermented foods, retort foods, confectionery, pharmaceuticals, bulbs, seeds, mushrooms and other packaging materials, wrap films, cell culture bags, and cell inspection films. , Heat-resistant vacuum forming containers, sugar beet containers, beet lids, baking cartons, various release films, and the like.

  Examples of films other than those described above include, for example, release films for flexible printed boards, release films for ACM boards, release films for rigid boards, release films for rigid flexible boards, release films for advanced composite materials, carbon fiber composites Release film for curing material, Release film for curing glass fiber composite, Release film for curing aramid fiber composite, Release film for curing nanocomposite, Release film for curing filler filler, Release for semiconductor sealing Mold film, release film for polarizing plate, release film for diffusion sheet, release film for prism sheet, release film for reflection sheet, cushion film for release film, release film for fuel cell, release for various rubber sheets Mold film, release film for urethane curing, release film for epoxy curing, solar cell Sealing sheet, solar cell back sheet, plastic film for solar cell, battery separator, separator for lithium ion battery, electrolyte membrane for fuel cell, adhesive / adhesive separator, light guide plate, optical disc, dicing tape / back grind tape・ Process substrate for semiconductors such as die-bonding film, double-layer FCCL, film for film capacitor ・ Adhesive material / Separator, adhesive film, stress relief film, film for pellicle, film for polarizing plate, protective film for polarizing plate, Protective films for liquid panels, protective films for optical components, protective films for lenses, protective films for electrical components and electrical appliances, protective films for mobile phones, protective films for PCs, protective films for touch panels, window glass protective films, baking coatings for Protective films such as film, masking film, capacitor film, capacitor film, tab lead film, fuel cell capacitor film, reflective film, diffusion film, laminate (including glass), radiation resistant film, gamma ray resistant film, porous film, Heat dissipation film / sheet, mold for manufacturing electronic component encapsulant, LED mold, high frequency circuit laminate, high frequency cable coating, optical waveguide substrate, glass fiber composite, carbon fiber composite, glass interlayer, laminated glass Film, building material window film, arcade dome, instrument panel skin, door trim skin, rear package trim skin, ceiling skin, rear pillar skin, gymnasium window glass substitute, LCD board film, bulletproof material, bulletproof glass film, heat shield Sheet, thermal barrier fill Release paper for synthetic leather, release paper for advanced composite materials, release paper for curing carbon fiber composite materials, release paper for curing glass fiber composite materials, release paper for curing aramid fiber composite materials, release paper for curing nanocomposite materials, filler Release paper such as release paper for curing filler, heat and water resistant photographic paper, packaging film, release film, breathable film, medical film and sheet, cell culture film and sheet, clear file, clear sheet, desk mat, Toys, shoe soles, shoe soles, shoe midsoles / inner soles, soles, sandals, chair skins, bags, school bags, jumper coats, wears, bands, bars, ribbons, notebook power bars, book covers, flooring , Gymnastic mats, health supplies (eg, non-slip mats / sheets, anti-tip films / mats / sheets), health equipment components, shock absorbing pads, protectors Protection (eg helmets Bok, guard), sporting goods (e.g. sports grip, protector) tarpaulins, building materials sheets, reflection films, synthetic paper, a display film, a display conductor film, such as a display barrier film.

  EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

[Synthesis of transition metal complexes]
(8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] Indene)) Synthesis of zirconium dichloride (catalyst A)

(1) Synthesis of 1-adamantylcyclopentadienyllithium Under a nitrogen atmosphere, a 200 ml three-necked flask was charged with 40 ml of tert-butyl methyl ether solution of 1.0 M ethylmagnesium bromide. While this solution was cooled in an ice bath, 2.64 g of cyclopentadiene was added dropwise over 20 minutes, the temperature was returned to room temperature, and the mixture was stirred for 17 hours to prepare Solution A.

  Under a nitrogen atmosphere, a 500 ml three-necked flask was charged with 200 ml of diisopropyl ether and 0.36 g of copper (II) trifluoromethanesulfonate. Under a water bath, the previously prepared solution A was added dropwise to this solution over 20 minutes. A solution prepared by dissolving 4.30 g of 1-bromoadamantane in 40 mL of diisopropyl ether was added dropwise and stirred at 70 ° C. for 10 hours. After cooling the reaction solution to room temperature, 200 ml of a saturated aqueous ammonium chloride solution was added in a water bath. The organic layer was separated, and the aqueous layer was extracted with 200 ml of hexane, and the organic liquid obtained by combining the extracted hexane with the previous organic layer was washed with water. The organic liquid was dried over magnesium sulfate, and then the solvent was distilled off. The obtained solid was purified using a silica gel column chromatograph to obtain 4.2 g of a crude product.

Under a nitrogen atmosphere, a 100 ml Schlenk flask was charged with 4.2 g of the obtained crude product and 20 mL of hexane. In an ice bath, 13.8 mL of 1.6 M n-butyllithium hexane solution was added dropwise to the solution over 20 minutes, and the mixture was returned to room temperature and stirred for 17 hours. A precipitate was collected from this reaction solution by filtration and washed with hexane to obtain 1-adamantylcyclopentadienyl lithium which was the target product. The yield was 2.70 g and the yield was 66%.
^The target product was identified from the measurement result of ¹ H-NMR. The measurement results are as follows.
¹ H-NMR (THF-d ₈ ): δ 5.57-5.55 (2H, m), 5.52-5.50 (2H, m), 1.96 (3H, s), 1.87 ( 6H, s), 1.74 (6H, s).

(2) Synthesis of 2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene 100 ml three-necked flask under nitrogen atmosphere To this was charged 40 ml of THF and 1.57 g of magnesium chloride. To this solution, a solution obtained by dissolving 3.09 g of 1-adamantylcyclopentadienyllithium in 10 ml of THF was added dropwise over 5 minutes, followed by stirring at room temperature for 2 hours and further at 50 ° C. for 3 hours. In an ice / acetone bath, a solution obtained by dissolving 1.96 g (15.75 mmol) of 1-acetylcyclohexene in 10 ml of THF was added dropwise over 10 minutes and stirred at room temperature for 19 hours. In an ice / acetone bath, 1.0 ml of acetic acid and 3.1 ml of pyrrolidine were charged and stirred at room temperature for 17 hours. Under an ice / acetone bath, 30 ml of a saturated aqueous ammonium chloride solution was added to this solution. After adding 100 ml of hexane to this solution, the organic layer is separated, and the aqueous layer is extracted with 200 ml of hexane, and the organic liquid obtained by combining the extracted hexane with the previous organic layer is washed twice with water. did. The organic liquid was dried over magnesium sulfate, and then the solvent was distilled off. The obtained solid was recrystallized from methanol to give the desired product 2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6,7,7a, 8-octahydro. Cyclopenta [a] indene was obtained. The yield was 2.134 g and the yield was 47%.
^The target product was identified from the measurement results of ¹ H-NMR and GC-MS. The measurement results are as follows.
¹ H-NMR (Toluene-d ₈ ): δ 6.06 (1H, s), 5.98 (1H, s), 2.88-2.78 (2H, m), 1.98-1.13 ( 26H, m).
GC-MS: m / Z = 306 (M ^<+> ).
(3) 8-Octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta

Synthesis of [a] indene) Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 1.546 g of octamethylfluorene and 40 ml of tert-butyl methyl ether. Under an ice / acetone bath, 2.62 ml of 1.6M n-butyllithium hexane solution was added dropwise to the solution over 15 minutes. The mixture was stirred for 22 hours while gradually returning to room temperature. To this solution was added 1.349 g of 2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene. After stirring at room temperature for 19 hours and further at 50 ° C. for 8 hours, the reaction solution was added to 100 ml of a saturated aqueous ammonium chloride solution. The organic layer was separated, and the aqueous layer was extracted with 100 ml of hexane, and the organic liquid obtained by combining the extracted hexane with the previous organic layer was washed twice with water. The organic liquid was dried over magnesium sulfate, and then the solvent was distilled off. By washing the obtained solid with acetone, the target product, 8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,5, 6,7,7a, 8-octahydrocyclopenta [a] indene). The yield was 1.51 g and the yield was 54%.
The target product was identified based on the FD-MS measurement results. The measurement results are as follows.
FD-MS: m / Z = 693 (M ^<+> ).
^From the measurement result of ¹ H-NMR, the obtained 8-octamethylfluoren-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 multiple isomers.

(4) Synthesis of Transition Metal Complex (Catalyst A) Under a nitrogen atmosphere, 8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene) 1.039 g, α-methylstyrene 0.47 ml, hexane 30 ml, cyclopentyl methyl ether 2.62 ml were charged. Under an oil bath at 25 ° C., 2.18 ml of a 1.6M n-butyllithium hexane solution was added dropwise to the solution over 10 minutes. After stirring at 50 ° C. for 4 hours, the precipitate was filtered and washed with hexane to obtain a pink powder. A 100 ml Schlenk tube was charged with 30 ml of this pink powder and diethyl ether. After this solution was cooled in a dry ice / acetone bath, 0.385 g (1.65 mmol) of zirconium tetrachloride was suspended in 30 ml of diethyl ether and added to this solution. Thereafter, the mixture was stirred for 16 hours while gradually warming to room temperature.

After distilling off the solvent under reduced pressure, soluble components were extracted from the residue using about 70 ml of dichloromethane. After the obtained extract was concentrated, 50 ml of hexane was added, and insoluble matters were removed by filtration. The solution was concentrated to about 10 ml and allowed to stand at −30 ° C. overnight. The precipitated powder was taken out by filtration and washed with hexane to obtain 0.384 g of an orange powder. The orange powder was dissolved by adding 5 ml of diethyl ether and allowed to stand at −30 ° C. overnight. The precipitated powder was taken out by filtration, washed with hexane, and the target product (8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4, 5,6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride was obtained. The yield was 0.220 g and the yield was 17%.
^The target product was identified from the measurement result of ¹ H-NMR. The measurement results are as follows.
¹ H-NMR (270 MHz, CDCl ₃ , TMS standard): δ 7.98 (1H, s), 7.86 (1H, s), 7.60 (1H, s), 7.37 (1H, s), 6.19 (1H, J = 1.6 Hz, d), 5.33 (1H, J = 1.6 Hz, d), 3.58-3.44 (2H, m), 2.35-2.28 (1H, m), 2.18 (3H, s), 1.94-1.18 (54H, m).

[Preparation of solid catalyst component]
In a three-necked flask equipped with a 100 mL stirrer sufficiently purged with nitrogen at 30 ° C., 32 mL of purified decane and solid polymethylaluminoxane (manufactured by Tosoh Finechem) were charged with 14.65 mmol in terms of aluminum atom. Into a suspension. 50 mg (0.059 mmol in terms of zirconium atom) of the previously synthesized catalyst (A) was added to the suspension as a 4.6 mmol / L toluene solution, and 12.75 mL of this solution was added with stirring. After 1.5 hours, stirring was stopped, and the obtained catalyst component was washed with 50 mL of decane three times by a decantation method and suspended in decane to obtain 50 mL of slurry liquid (B). In this catalyst component, the Zr loading was 100%.

[Preparation of prepolymerization catalyst component]
To the slurry liquid (B) prepared above, 2.0 mL of decane solution of diisobutylaluminum hydride (2.0 mmol / mL in terms of aluminum atoms) and 7.5 mL of 3-methyl-1-pentene (under an aluminum stream) ( 5.0 g) was charged. After 1.5 hours, stirring was stopped, and the resulting prepolymerized catalyst component was washed with 50 mL of decane three times by a decantation method. This prepolymerization catalyst component was suspended in decane to obtain 50 mL of decane slurry (C). The concentration of the prepolymerization catalyst component in the decane slurry (C) was 20 g / L, 1.05 mmol-Zr / L, and the Zr recovery rate was 90%.

[Production Example 1] (Production of polymer [X-1])
Purified decane 425 mL, diisobutylaluminum hydride decane solution (2.0 mmol / mL in terms of aluminum atoms) 0.5 mL (1 mol) in a SUS polymerizer equipped with a stirrer with an internal volume of 1 L at room temperature under a nitrogen stream I was charged. Next, 0.0005 mmol of the previously prepared decane slurry solution (C) of the prepolymerized catalyst component was added in terms of zirconium atom, and hydrogen was charged at 50 NmL (first hydrogen charging). Subsequently, a mixed solution of 250 mL of 4-methyl-1-pentene and 3.3 mL of 1-decene was continuously charged into the polymerization reactor at a constant rate over 2 hours. This charging start time was regarded as the start of polymerization, and the temperature was raised to 45 ° C. over 30 minutes from the start of polymerization, and then kept at 45 ° C. for 4 hours. 3 hours after the start of polymerization, 90 NmL of hydrogen was charged (second hydrogen charging). After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, and after depressurization, the polymerization liquid containing a white solid was immediately filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80 ° C. for 8 hours to obtain a polymer [X-1]. The yield was 131 g. Table 1 shows the results of measurement of ¹³ C-NMR, GPC, MFR and decane soluble part of the polymer [X-1]. In the table, “-” means that there is no data.

[Production Example 2] (Production of polymer [X-2])
The polymer [X-2] changes the proportion of 4-methyl-1-pentene, 1-decene, 1-hexadecene, 1-octadecene and hydrogen in accordance with the method of Comparative Example 7 of International Publication No. 2006/054613. Was obtained by The results of ¹³ C-NMR, GPC, MFR and decane soluble part measurements are shown in Table 1. In the table, “-” means that there is no data.

<Polymer [X-1] and [X-2] Evaluation Pellet Preparation>
Polymerization was carried out a plurality of times as necessary to prepare a sufficient amount of polymer for pellet production. For 100 parts by mass of each polymer, 0.1 part by mass of tri (2,4-di-tert-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl-3- (4 as a heat stabilizer 0.1 parts by mass of '-hydroxy-3', 5'-di-t-butylphenyl) propinate was blended. Thereafter, using a twin screw extruder BT-30 (screw system 30 mmφ, L / D 46) manufactured by Plastic Engineering Laboratory Co., Ltd., conditions of set temperature 260 ° C., resin extrusion rate 60 g / min, and rotation speed 200 rpm To obtain pellets for evaluation.

  The obtained pellets for evaluation were subjected to DSC measurement and melt tension measurement by the methods described later. The results are shown in Table 1. In the table, “-” means that there is no data.

<Polyolefin (Y)>
Prime Polypro (trademark) E200GP, which is a homopolypropylene manufactured by Prime Polymer, was used as the polyolefin (Y). MFR under a load of 2.16 kg at 230 ° C. was 2 g / 10 minutes.

<Create film>
[Example 1]
The polymer [X-1] and the polyolefin (Y) were dry blended at a ratio of 70 parts by mass to 30 parts by mass. 0.1 parts by mass of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl-3- (4 ′ as a heat stabilizer) with respect to 100 parts by mass of the blend 0.1 part by mass of -hydroxy-3 ', 5'-di-t-butylphenyl) propinate was blended. Thereafter, using a twin screw extruder BT-30 (screw system 30 mmφ, L / D 46) manufactured by Plastic Engineering Laboratory Co., Ltd., conditions of set temperature 260 ° C., resin extrusion rate 60 g / min, and rotation speed 200 rpm To obtain a resin composition. Resin composition Using this, a coat hanger type T die (lip shape 270 × 0.8 mm) is attached to a single screw extruder (screw diameter 20 mmφ, L / D 28) manufactured by Thermo Plastic Co., Ltd., and the die temperature Molding was performed at a roll temperature of 70 ° C. and a winding speed of 2.0 m / min under the condition of 270 ° C. to obtain a film having a thickness of 50 μm.

  The resulting film was evaluated for surface gloss, film tensile elongation / strength, film impact, and tear strength by the methods described below. The evaluation results are shown in Table 2.

[Comparative Example 1]
A film having a thickness of 50 μm was obtained in the same procedure as in Example 1 except that the polymer [X-2] was used instead of the polymer [X-1]. The evaluation results are shown in Table 2.

[Comparative Example 2]
A film having a thickness of 50 μm was obtained in the same procedure as in Example 1 except that the polymer used was changed to the polymer [A-2] alone (100 parts by mass). The evaluation results are shown in Table 2.
Hereinafter, the evaluation method of a polymer, an evaluation pellet, and a film will be specifically described.

[Content of constituent unit]
A structural unit derived from at least one olefin selected from ethylene in a 4-methyl-1-pentene polymer and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (comonomer) ) Content was calculated from the ¹³ C-NMR spectrum with the following apparatus and conditions.

Using a Bruker BioSpin AVANCE III cryo-500 type nuclear magnetic resonance apparatus, the solvent is an o-dichlorobenzene / benzene-d ₆ (4/1 v / v) mixed solvent, the sample concentration is 55 mg / 0.6 mL, and the measurement temperature Is 120 ° C, the observation nucleus is ¹³ C (125 MHz), the sequence is single pulse proton broadband decoupling, the pulse width is 5.0 μsec (45 ° pulse), the repetition time is 5.5 seconds, and the number of integrations is 64 times. 128 ppm of benzene-d ₆ was measured as a reference value for chemical shift. Using the integral value of the main chain methine signal, the content of the comonomer-derived structural unit was calculated according to the following formula.

Content of comonomer-derived structural unit (%) = [P / (P + M)] × 100
Here, P represents the total peak area of the comonomer main chain methine signal, and M represents the total peak area of the 4-methyl-1-pentene main chain methine signal.

[Mesodyad fraction]
The meso-dyad isotacticity (meso-dyad fraction) of 4-methyl-1-pentene polymer represents any two head-to-tail linked 4-methyl-1-pentene unit chains in the polymer chain in a planar zigzag structure Was defined as a ratio in which the directions of isobutyl branching were the same, and were determined from the ¹³ C-NMR spectrum by the following formula.

Isodiad tacticity (%) = [m / (m + r)] × 100
(In the formula, m and r represent the absorption intensity derived from the main chain methylene of 4-methyl-1-pentene units bonded in a head-to-tail manner represented by the following formula.)

^{The 13} C-NMR spectrum was measured using an AVANCE III cryo-500 type nuclear magnetic resonance apparatus manufactured by VALQUA BioSpin, the solvent was an o-dichlorobenzene / benzene-d6 (4/1 v / v) mixed solvent, and the sample concentration was 60 mg / 0.6 mL, measurement temperature is 120 ° C., observation nucleus is ¹³ C (125 MHz), sequence is single pulse proton broadband decoupling, pulse width is 5.0 μsec (45 ° pulse), repetition time is 5.5 seconds, 128 ppm of benzene-d6 was measured as a reference value for chemical shift.

  For the peak region, the region of 41.5 to 43.3 ppm was divided by the minimum points of the peak profile, and the high magnetic field side was classified as the first region and the low magnetic field side was classified as the second region.

  In the first region, the main chain methylene in two chains of 4-methyl-1-pentene units represented by (m) resonates, but the integrated value regarded as a 4-methyl-1-pentene homopolymer is “m”. It was. In the second region, the main chain methylene in the 2-methyl-1-pentene unit 2 chain represented by (r) resonated, and the integrated value was “r”. In addition, less than 0.01% was made into the detection limit or less.

[Mw / Mn, Mz / Mw, ratio of polymer having a molecular weight of 1 × 10 ⁶ or more]
The weight average molecular weight (Mw), number average molecular weight (Mn), and Z average molecular weight (Mz) were measured by GPC. GPC measurement was performed under the following conditions. Moreover, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the Z average molecular weight (Mz) were determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.

(Measurement condition)
Apparatus: Gel permeation chromatograph HLC-8321 GPC / HT type (manufactured by Tosoh Corporation)
Organic solvent: o-dichlorobenzene Column: 2 TSKgel GMH6-HT, 2 TSKgel GMH6-HTL columns (both manufactured by Tosoh Corporation)
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 coefficient of the Mark-Houwink viscosity formula was used for calculation of general-purpose calibration. The values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970)) were used for the Mark-Houwink coefficient of PS, respectively.
Further, in the PS-converted GPC chart, the ratio of the integrated area value of 1,000,000 or more components to the total area of the chart is defined as the component ratio of 1 × 10 ⁶ or more.

[Melt flow rate (MFR)]
The melt flow rate (MFR) was measured under the conditions of 260 ° C. and 5 kg load according to ASTM D1238.

[Amount of decane soluble part]
200 mL of n-decane was added to 5 g of each polymer and dissolved by heating at 145 ° C. for 1 hour. It was cooled to 23 ° C. and left for 30 minutes. Thereafter, the precipitate (n-decane insoluble part) was filtered off. The filtrate was placed in about 3 times the amount of acetone to precipitate the components dissolved in n-decane. The precipitate was filtered off from acetone and dried. The mass of the precipitate was measured. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane soluble part was determined by the following formula.
n-decane soluble part amount (% by mass) = [amount of precipitated substance / polymer mass] × 100

[Melting point, heat of fusion]
Using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., about 5 mg of sample was put in an aluminum pan for measurement, and the temperature was raised to 280 ° C. at 10 ° C./min. After maintaining at 280 ° C. for 5 minutes, the temperature was lowered to 20 ° C. at 10 ° C./min. After maintaining at 20 ° C. for 5 minutes, the temperature was raised to 280 ° C. at 10 ° C./min. The temperature at which the peak of the crystal melting peak observed at the second temperature increase appears was defined as the melting point. Further, the heat of fusion was calculated from the integrated value of the crystal melting peak.

[Melting tension]
Capillograph 1D, an apparatus of Toyo Seiki Seisakusho, was used for melt tension measurement. After the sample was charged into a melting furnace (diameter 9.55 mm) set at 260 ° C and sufficiently melted, it passed through a capillary with L / D 8 / 2.095 mm and inflow angle 180 ° at an extrusion speed of 15 mm / min. Then, a pulley fixed at a position of 58 cm from the lower part of the capillary was passed, and when the molten resin was wound up at a speed of 15 m / min, the stress applied to the pulley portion was measured, and the stress was taken as the melt tension.

[Vicat softening temperature]
For a press sheet having a thickness of 3 mm, a Vicat softening temperature test was performed in a silicone oil using a tester manufactured by Yasuda Seiki Co., Ltd. at a heating rate of 50 ° C. per hour and a test load of 10 N in accordance with ASTM D1525.

[gross]
The gloss was measured at a room temperature with a gloss angle of 60 ° using a gloss meter using a film having a thickness of 50 μm obtained by the above film forming method in accordance with JIS K7105 as a test piece.

[Film tensile elongation]
The tensile elongation and initial elastic modulus, which are tensile properties, were measured at a tensile speed of 200 mm / min using an all-purpose tensile tester 3380 manufactured by Instron Co., Ltd., using the above-mentioned film as a test piece in accordance with JIS K678.

[Film Impact]
What cut | disconnected the film in the strip shape of width 100mm x length 100mm was used as a test piece. Under the condition of 23 ° C., the test piece was sandwiched between metal chucks, and a cylindrical measuring jig having a tip diameter of 12.7 mm was dropped from a height of 50 cm obliquely. And the impact strength (fracture energy) to the test piece when contact was recognized to the test piece visually was measured.

[Tear strength]
In the present invention, the tear strength was measured by Elmendorf tear strength. The value measured based on JIS K7128-2 (1998) on the conditions of measurement temperature 23 degreeC.

Claims (4)

The content of the structural unit derived from 4-methyl-1-pentene is 90 to 100 mol%, and at least one selected from ethylene and α-olefins other than 4-methyl-1-pentene having 3 to 20 carbon atoms. The content of the structural unit derived from olefin is 0 to 10 mol%, and satisfies the following requirements (X-1) to (X-4): 4-methyl-1-pentene polymer (X) 60 to 95 mass And 4 to 40 parts by mass of polyolefin (Y) satisfying the following requirement (Y-1) different from the 4-methyl-1-pentene polymer (X) (where (X) and (Y) The film or sheet containing the resin composition (A) containing 100 mass parts).
(X-1) Meso-dyad fraction (m) measured by ¹³ C-NMR is in the range of 98 to 100%.
(X-2) Melt flow rate (MFR) measured in accordance with ASTM D1238 under a load condition of 260 ° C. and 5 kg is in the range of 0.1 to 100 g / 10 min.
(X-3) 23 degreeC decane soluble part amount is 5 mass% or less.
(X-4) The heat of fusion and melting point measured by differential scanning calorimetry (DSC) satisfy the following requirements (i) and (ii).
(I) The following formula (1) is established.
ΔHm ≧ 0.5 × Tm−76 (1)
(In the formula (1), the heat of fusion is ΔHmJ / g, and the melting point is Tm ° C.)
(Ii) Melting | fusing point exists in the range of 200-260 degreeC.
(Y-1) The melting point measured by differential scanning calorimetry (DSC) is 100 ° C. or higher.   The film or sheet according to claim 1, wherein the polyolefin (Y) is polypropylene. The film or sheet according to claim 1 or 2, wherein the polypropylene (Y) satisfies the following requirements (Y-2) and (Y-3).
(Y-2) Content of the structural unit derived from propylene is 90 mol% or more.
(Y-3) MFR (230 ° C., 2.16 kg load) is in the range of 0.1 to 100 g / 10 min. The film or sheet according to any one of claims 1 to 3, wherein the 4-methyl-1-pentene polymer (X) satisfies the following requirements (X-5) and (X-6).
(X-5) The ratio (Mz / Mw) of the Z average molecular weight Mz and the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is in the range of 2.5-20.
(X-6) The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) is in the range of 3.6-30.