JP7288325B2 - Polymer composition and molded article containing 4-methyl-1-pentene polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymer composition and molded article containing a 4-methyl-1-pentene polymer.

4-Methyl-1-pentene polymers obtained by copolymerizing 4-methyl-1-pentene with α-olefins such as 1-butene, 1-pentene and 1-hexene are used in medical instruments and medical packaging materials. , laboratory equipment, cosmetic containers, etc. Various studies have been made on 4-methyl-1-pentene-based polymers (see Patent Documents 1 to 3).

WO2005/121192 JP 2008-144155 A JP 2018-162408 A

A molded article formed using a 4-methyl-1-pentene polymer may not have sufficient impact resistance, and there is a demand for improving the impact resistance. In addition, in various applications where 4-methyl-1-pentene-based polymers are used, molded articles are often required to have heat resistance, transparency and rigidity.
Patent Document 3 discloses a 4-methyl-1-pentene polymer composition having high impact resistance and heat resistance while having transparency and rigidity. , there is room for further improvement.

The present invention has been made in view of the above, and an object of the present invention is to provide a polymer composition and a molded article which are excellent in well-balanced heat resistance, rigidity, transparency and impact resistance.

As a result of intensive studies on methods for solving the above problems, the present inventors have found that the above problems can be solved by using a specific composition, and have completed the present invention.
A configuration example of the present invention is as follows.

[1] 70.0 to 85.0% by mass of a 4-methyl-1-pentene (co)polymer (A) that satisfies the following requirement (Aa);
30.0 to 15.0% by mass of 4-methyl-1-pentene copolymer (B) that satisfies the following requirements (Ba) (provided that (co)polymer (A) and copolymer (B) The total is 100% by mass) and
A polymer composition (X) that satisfies the following requirement (X-1), comprising:
Requirement (Aa): The content of structural units derived from 4-methyl-1-pentene is 96.0 to 100 mol%, and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1 -The content of structural units derived from olefins selected from the group consisting of 4.0 to 0 mol% Requirement (Ba): of structural units derived from 4-methyl-1-pentene The content is 85.0 mol% or more and less than 96.0 mol%, and the content of structural units derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 4 more than 0 mol % and 15.0 mol % or less Requirement (X-1): The intrinsic viscosity of each of the (co)polymer (A) and copolymer (B) measured in decalin at 135 ° C. [η _A ] and [η _B ] satisfy the following formula: 0.7≦1/[η _A ]×([η _B ]/[η _A ]) ^0.84 ≦5.3

[2] The polymer composition (X) according to [1], which satisfies the following requirement (X-2).
Requirement (X-2): When 100 island phases with a sea-island structure are observed, and the average value obtained by adding the longest diameter and shortest diameter of each of the top 10 island phases with the largest area is taken as the dispersion diameter, Dispersion diameter is 0.3 to 3.0 μm

[3] The polymer composition (X) according to [1] or [2], which satisfies at least one of the following requirements (X-3) to (X-6).
Requirement (X-3): Using a molded body of composition (X) with a thickness of 2 mm, the high-speed surface impact strength at 23 ° C. measured in accordance with JIS K 7211 is 4 to 20 J. Requirement (X-4): Using a molded body of composition (X) with a thickness of 3 mm, it does not break when subjected to an Izod impact test at 23 ° C. in accordance with ASTM D256 Requirement (X-5): Molding of composition (X) with a thickness of 2 mm Using a body, the total light transmittance measured in accordance with JIS K 7361 is 90 to 98.0% Requirement (X-6): Using a 2 mm thick molded body of composition (X), ASTM D638 The tensile modulus measured according to the standard is 1000 to 2000 MPa

[4] A molded article containing the polymer composition (X) according to any one of [1] to [3].

According to the present invention, a polymer composition that is excellent in well-balanced heat resistance, rigidity, transparency and impact resistance without impairing the heat resistance, rigidity and transparency of a 4-methyl-1-pentene polymer and Molded bodies can be provided.

<<Polymer composition (X)>>
The polymer composition (X) (hereinafter also simply referred to as "composition (X)") according to the present invention is
70.0 to 85.0% by mass of a 4-methyl-1-pentene (co)polymer (A) that satisfies the following requirements (Aa) (hereinafter also simply referred to as “polymer (A)”);
A 4-methyl-1-pentene copolymer (B) other than the (co)polymer (A) (hereinafter also simply referred to as "polymer (B)") that satisfies the following requirement (Ba)30. 0 to 15.0% by mass (where the total of the polymers (A) and (B) is 100% by mass);
and satisfy the following requirement (X-1).

The content of the polymer (A) in the composition (X) is 70.0 to 85.0% by mass, preferably 70.0%, based on the total 100% by mass of the polymers (A) and (B). ~80.0% by mass, more preferably 72.0 to 77.0% by mass.
The content of the polymer (B) in the composition (X) is 30.0 to 15.0% by mass, preferably 30.0%, based on the total 100% by mass of the polymers (A) and (B). ~20.0% by mass, more preferably 28.0 to 23.0% by mass.
When the contents of the polymers (A) and (B) are within the above range, the heat resistance, rigidity, transparency and impact resistance are well balanced, and in particular the following requirements (X-5) to (X-8) can be easily obtained.
If the content of the polymer (A) is below the above range, the heat resistance, rigidity, and transparency tend to be lowered, and if the content of the polymer (A) exceeds the above range, the impact resistance is lowered. There is a tendency.

The total content of the polymers (A) and (B) with respect to 100% by mass of the composition (X) is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. , the upper limit is 100% by mass.
When the total content of the polymers (A) and (B) is within the above range, it is possible to easily obtain a composition and a molded article that sufficiently exhibit the physical properties of the 4-methyl-1-pentene polymer. can.

The composition (X) is not particularly limited as long as it satisfies the following requirements (X-1), and further preferably satisfies at least one of the following requirements (X-2) to (X-8), especially all of them. It is preferable to satisfy the requirements of

[Requirements (X-1)]
Requirement (X-1) is that the intrinsic viscosities [η _A ] and [η _B ] of the (co)polymer (A) and copolymer (B), respectively, measured in decalin at 135° C. are given by the following formula: to be satisfied. The intrinsic viscosity can be specifically measured by the method described in Examples below.
0.7≦1/[η _A ]×([η _B ]/[η _A ]) ^0.84 ≦5.3

The left side of the above formula is preferably 1.0, more preferably 1.5, and the right side of the above formula is preferably 5.0, more preferably 4.5.
The above formula is based on Wu's formula relating to the size of the islands in the sea-island structure. By satisfying this formula, it is possible to easily obtain a composition or molded article having particularly excellent impact resistance. That is, by controlling [η] of the specific polymer to be used so as to satisfy the above formula, the size of the islands can be controlled and the impact resistance can be improved.

[Requirements (X-2)]
Requirement (X-2) is that when 100 island phases with a sea-island structure are observed, and the averaged value obtained by adding the longest diameter and shortest diameter of each of the top 10 island phases with the largest area is taken as the dispersion diameter, Its dispersion diameter is specified to be 0.3 to 3.0 μm. Specifically, the size (diameter) of the island phase can be measured by the method described in Examples below.
Specifically, the dispersion diameter is calculated by the formula "(total length of 10 longest diameters (μm)+total length of 10 shortest diameters (μm))/20".
The dispersion diameter is preferably 0.3-2.8 μm, more preferably 0.4-2.6 μm.
When the dispersion diameter is within the above range, that is, when the island size is within the above range, it is possible to easily obtain a composition or molded article having particularly excellent impact resistance.

[Requirements (X-3)]
Requirement (X-3) specifies that the high-speed surface impact strength at 23° C. measured according to JIS K 7211 is 4 to 20 J using a 2 mm-thick molded article of composition (X). The high-speed surface impact strength can be specifically measured by the method described in Examples below.
The high speed surface impact strength is preferably 5 to 19J, more preferably 6 to 18J.
It can be said that the fact that the high-speed surface impact strength is within the above range means that the impact resistance is excellent.

[Requirements (X-4)]
Requirement (X-4) stipulates that a molded body of composition (X) with a thickness of 3 mm is not destroyed when subjected to an Izod impact test at 23° C. according to ASTM D256. The Izod impact test can be specifically measured by the method described in Examples below.
The fact that the specimen was not destroyed in the Izod impact test means that the specimen has excellent impact resistance.

[Requirements (X-5)]
Requirement (X-5) defines that the total light transmittance measured according to JIS K 7361 is 90 to 98.0% using a 2 mm-thick molded body of composition (X). The total light transmittance can be specifically measured by the method described in Examples below.
The total light transmittance is preferably 90.0-95.0%, more preferably 90.0-93.5%.
It can be said that the fact that the total light transmittance is within the above range means that the transparency of the 4-methyl-1-pentene polymer is not impaired and the transparency is excellent.

[Requirements (X-6)]
Requirement (X-6) specifies that the tensile modulus measured according to ASTM D638 is 1000 to 2000 MPa using a molded body of composition (X) having a thickness of 2 mm. Specifically, the tensile modulus can be measured by the method described in Examples below.
The tensile modulus is preferably 1200-1700 MPa, more preferably 1300-1500 MPa.
It can be said that the fact that the tensile modulus is within the above range means that the rigidity of the 4-methyl-1-pentene polymer is not impaired and the rigidity is excellent.

[Requirements (X-7)]
Requirement (X-7) stipulates that a 1/4 inch thick molded body of composition (X) must have a deflection temperature under load of 80° C. or higher as measured according to ASTM D648. Specifically, the deflection temperature under load can be measured by the method described in Examples below.
The deflection temperature under load is preferably 83°C or higher, more preferably 85°C or higher, and the upper limit is not particularly limited, but is 110°C, for example.
It can be said that the fact that the deflection temperature under load is within the above range means that the heat resistance of the 4-methyl-1-pentene polymer is not impaired and the heat resistance is excellent.

[Requirements (X-8)]
Requirement (X-8) specifies that the Vicat softening temperature measured according to ASTM D1525 is 100° C. or higher using a 3 mm-thick molded body of composition (X). The Vicat softening temperature can be specifically measured by the method described in Examples below.
The Vicat softening temperature is preferably 140°C or higher, more preferably 145 to 160°C.
It can be said that the fact that the Vicat softening temperature is in the above range means that the heat resistance of the 4-methyl-1-pentene polymer is not impaired and the heat resistance is excellent.

The melting point (Tm) of the composition (X) measured by DSC is preferably 200 to 260° C., more preferably 200 to 250° C., from the viewpoint that a composition having excellent heat resistance can be easily obtained. More preferably 205 to 250°C, particularly preferably 210 to 245°C.
Specifically, the Tm can be measured by the method described in Examples below.

The comonomer content of composition (X) is preferably 1.5 to 5.0 mol %, more preferably 1.7 to 4.5 mol %, particularly preferably 1.9 to 4.0 mol % .
When the comonomer content is within the above range, impact resistance, rigidity, heat resistance and transparency are well balanced. If the comonomer content is less than the above range, the impact resistance tends to decrease, and if the comonomer content exceeds the above range, the rigidity, heat resistance and transparency tend to decrease.
The comonomer content is the weight of the composition (X) when the total amount of the structural units constituting the polymers (A) and (B) in the composition (X) is 100 mol%. It refers to the total content of structural units other than structural units derived from 4-methyl-1-pentene, which constitute coalescence (A) and (B). Specifically, the content of structural units other than the structural unit derived from 4-methyl-1-pentene is a mass% of the polymer (A) in which the content of structural units other than the structural unit derived from A is 1 mol%, and the structural unit derived from 4-methyl-1-pentene The comonomer content in the composition containing b mass% (where a + b = 100) of the polymer (B) having a content of B1 mol% of the structural unit other than can do.
A1 and B1 can be specifically measured by the method described in the Examples below.

<4-methyl-1-pentene (co)polymer (A)>
The polymer (A) is not particularly limited as long as it satisfies the following requirements (Aa), and is a homopolymer of 4-methyl-1-pentene (that is, the content of structural units derived from 4-methyl-1-pentene is 100 mol %), or copolymers of 4-methyl-1-pentene and other olefins or monomers. Furthermore, the polymer (A) may be a graft-modified product obtained by using a homopolymer or copolymer of these as a modified product and graft-modified using a polar monomer or a silane coupling agent.
The polymer (A) used in the composition (X) may be of one type or two or more types.

[Requirements (Aa)]
Requirement (Aa) is that the content of structural units (U1) derived from 4-methyl-1-pentene is 96.0 to 100 mol% with respect to all structural units contained in polymer (A). , and the content of the structural unit (U2) derived from an olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 4.0 to 0 mol%. stipulate that there is
The content of the structural unit (U1) is preferably 97 to 100 mol%, more preferably 98.0 to 99.9 mol%, from the viewpoint of excellent transparency and heat resistance in a well-balanced manner. The content of U2) is preferably 0 to 3.0 mol %, more preferably 0.1 to 2.0 mol %.
The content of the structural unit can be specifically measured by the method described in Examples below, and can be adjusted by adjusting the amounts of 4-methyl-1-pentene and the olefin added during the polymerization reaction.

Specific examples of the olefin to be the structural unit (U2) include 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, 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 are preferred, and 1-hexene, 1-hexadecene and 1-octadecene are particularly preferred from the viewpoints of transparency and handling during molding.
One of these olefins may be used, or two or more thereof may be used.

The polymer (A) may have constitutional units derived from monomers other than 4-methyl-1-pentene and the olefin as long as the effects of the present invention are not impaired.
The upper limit of the content of the structural unit derived from the other monomer is, for example, 12.2 parts by mass or less, preferably 6 parts by mass or less, with respect to the total 100 parts by mass of the structural units (U1) and (U2). be.

The intrinsic viscosity [η _A ] of the polymer (A) measured in decalin at 135° C. is preferably 0.5 to 5.0 dl/g, more preferably 0.7 to 4.0 dl/g, still more preferably is 0.7 to 3.0 dl/g, particularly preferably 0.8 to 2.0 dl/g.
When [η _A ] is within the above range, it is preferable from the viewpoint of resin fluidity during molding of the composition (X).
[η _A ] can be adjusted by appropriately selecting the hydrogen concentration and pressure of the polymerization system.

The melting point (Tm) of the polymer (A) measured by DSC is preferably 220 to 250° C., more preferably 225 to 250° C., from the viewpoint that a composition having excellent heat resistance can be easily obtained. More preferably 228 to 245°C, particularly preferably 230 to 245°C.
The Tm is determined by differential scanning calorimetry (heating rate: 10° C./min). The Tm can be arbitrarily adjusted by appropriately selecting the comonomer species and its amount.

<4-methyl-1-pentene copolymer (B)>
The polymer (B) is a polymer other than the polymer (A), is not particularly limited as long as it satisfies the following requirements (Ba), and is a copolymer of 4-methyl-1-pentene with other olefins or monomers. A polymer etc. are mentioned. Further, the polymer (B) may be a graft-modified product obtained by graft-modifying this copolymer with a polar monomer or a silane coupling agent.
The polymer (B) used in the composition (X) may be of one type or two or more types.

[Requirements (B-a)]
Requirement (Ba) is that the content of structural units (U3) derived from 4-methyl-1-pentene is 85.0 mol% or more and 96.0 with respect to all structural units contained in the polymer (B). Less than mol%, the content of structural units (U4) derived from olefins selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 4.0 It is specified to be more than 15.0 mol % and not more than 15.0 mol %.
The content of the structural unit (U3) is preferably 87.0 to 94.0 mol%, more preferably 89.0 to 93.0 mol%, from the viewpoint of better impact resistance, etc., and the structural unit ( The content of U4) is preferably 13.0 to 6.0 mol%, more preferably 11.0 to 7.0 mol%.
The content of the structural unit can be measured by IR or ¹³ C-NMR, and specifically can be measured by the method described in the following examples, and 4-methyl-1-pentene and It can be adjusted by the amount of the olefin.

Examples of α-olefins other than 4-methyl-1-pentene having 3 to 20 carbon atoms include 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, α-olefins other than 4-methyl-1-pentene having 6 to 20 carbon atoms are preferable, and specifically, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, Examples include 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene, and 1-hexene, 1-hexadecene and 1-octadecene are particularly preferred in terms of transparency and handling during molding.
One type of olefin may be used as the structural unit (U4), or two or more types may be used.

The polymer (B) may have constitutional units derived from monomers other than 4-methyl-1-pentene and the olefin as long as the effects of the present invention are not impaired.
The upper limit of the content of the structural unit derived from the other monomer is, for example, 37 parts by mass or less, preferably 30 parts by mass or less with respect to a total of 100 parts by mass of the structural units (U3) and (U4).

The intrinsic viscosity [η _B ] of the polymer (B) measured in decalin at 135° C. is preferably 2.0 to 6.0 dl/g, more preferably 3.0 to 5.5 dl/g, still more preferably is 3.5 to 5.3 dl/g, particularly preferably 4.0 to 5.0 dl/g.
When [η _B ] is within the above range, a composition having excellent moldability and flexibility can be easily obtained.
[η _B ] can be adjusted by appropriately selecting the hydrogen concentration and pressure of the polymerization system.

The melting point (Tm) of the polymer (B) as measured by DSC is preferably in the range of less than 220° C. or The point is that no peak indicating the melting point appears in the DSC measurement. If Tm is present, its temperature is more preferably less than 160°C, more preferably less than 155°C.
The Tm is determined by differential scanning calorimetry (heating rate: 10° C./min). The Tm can be arbitrarily adjusted by appropriately selecting the comonomer species and its amount.

[Method for producing polymers (A) and (B)]
The method for producing the polymers (A) and (B) is not particularly limited, and for example, the methods described in WO 01/27124, WO 14/050817, etc. can be employed.
Specifically, the polymers (A) and (B) can be obtained by polymerizing predetermined monomers in the presence of an olefin polymerization catalyst, which will be described later.

As the olefin polymerization catalyst,
a bridged metallocene compound (A);
(b-1) an organoaluminum oxy compound, (b-2) a compound that forms an ion pair by reacting with the metallocene compound (A), and (b-3) at least one selected from an organoaluminum compound a compound (B);
A catalyst containing is preferred.

- Bridged metallocene compound (A)
As the bridged metallocene compound (A), a compound represented by the following formula [A1] is preferable, and a compound represented by the following formula [A2] is more preferable.

In formula [A1], M is a transition metal of Group 4 of the periodic table, such as a titanium atom, a zirconium atom or a hafnium atom, and Q is independently a halogen atom, a hydrocarbon group, or a neutral having 10 or less carbon atoms. is a conjugated or non-conjugated diene, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons, j is an integer from 1 to 4, and ^RA and ^RB are each independently , M is a mononuclear or polynuclear hydrocarbon residue capable of forming a sandwich structure with M, Y is a carbon atom or a silicon atom, R ^C and R ^D are each independently a hydrogen atom, a hydrocarbon group , a silicon-containing group, a halogen atom or a halogen-containing hydrocarbon group, and R ^C and R ^D may combine with each other to form a ring.

In 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 each independently a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom or It is a halogen-containing hydrocarbon group, of which two adjacent ones may be bonded to each other to form a ring. M is a transition metal of Group 4 of the periodic table, Q is independently a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anion ligand, or a lone electron pair and j is an integer of 1-4.

Among the crosslinked metallocene compounds represented by the formula [A2], the crosslinked metallocene compounds represented by the following formula [A3] are preferred in terms of polymerization characteristics, availability, and ability to easily synthesize a polymer that satisfies the above requirements. Especially preferred.

In 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 each independently a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom or It is a halogen-containing hydrocarbon group, and two adjacent groups may combine with each other to form a ring. M is a transition metal of Group 4 of the periodic table, n is an integer of 1 to 3, Q is independently a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, It is an anionic ligand or a neutral ligand that can be coordinated with a lone pair of electrons, and j is an integer of 1-4.

Examples of the hydrocarbon group include one or more hydrogen atoms possessed by a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a saturated hydrocarbon group. is substituted with a cyclic unsaturated hydrocarbon group. The number of carbon atoms in the hydrocarbon group is generally 1-20, preferably 1-15, more preferably 1-10.

Linear hydrocarbon groups include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl straight-chain alkyl groups such as groups, n-decanyl groups; and straight-chain alkenyl groups such as allyl groups.

Branched hydrocarbon groups include, for example, isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1 -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group and other branched alkyl groups.

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

Examples of cyclic unsaturated hydrocarbon groups include phenyl, tolyl, naphthyl, biphenyl, phenanthryl, anthracenyl and other aryl groups; cyclohexenyl and other cycloalkenyl groups; 5-bicyclo[2.2. 1] polycyclic unsaturated alicyclic groups such as hept-2-enyl (norbornenyl) group.

Examples of the group obtained 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. A group obtained by substituting one or more hydrogen atoms of an alkyl group such as a group with an aryl group.

_Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, and the like. an alkyl group or a phenyl group of 1 to 15).

Examples of the halogen-containing hydrocarbon group include groups in which one or more hydrogen atoms of the hydrocarbon group, such as a trifluoromethyl group, are substituted with halogen atoms.

The halogen atom includes 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 adjacent substituents (e.g., 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 together to form a ring, and such rings may be formed at two or more locations in the molecule. may exist.
Examples of the ring (spiro ring, additional ring) formed by bonding the 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, preferably a cyclohexane ring, a benzene ring and a hydrogenated benzene ring. Moreover, such a ring structure may further have a substituent such as an alkyl group on the ring.

From the viewpoint of stereoregularity, R ^1b is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, further preferably not an aryl group, and a linear hydrocarbon group. A group, branched hydrocarbon group or cyclic saturated hydrocarbon group is particularly preferred, and a group in which the carbon having a free valence (the carbon bonded to the cyclopentadienyl ring) is a tertiary carbon is particularly preferred. .

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, and more preferably. is a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, a group in which the carbon having a free valence is a tertiary carbon, such as a 1-adamantyl group, particularly preferably a tert-butyl group, 1-adamantyl is the base.

In formula [A3], the fluorene ring portion is not particularly limited as long as it has 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 hydrogen atoms or hydrocarbon groups, more preferably hydrocarbon groups, still more preferably hydrocarbon groups having 1 to 20 carbon atoms. In addition, R ^2b and R ^3b may combine with each other to form a ring, and R ^6b and R ^7b may combine with each other to form a ring. Examples of such substituted fluorenyl groups 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 groups, particularly preferably 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro- It is a 1H-dibenzo[b,h]fluorenyl group.

R ^8b is preferably a hydrogen atom.
R ^9b is more preferably a hydrocarbon group, 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, Particularly preferably, R ^9b is an alkyl group having 2 or more carbon atoms. From the viewpoint of synthesis, R ^10b and R ^11b are also preferably hydrogen atoms.

Further, when n=1, it is more preferable that R ^9b and R ^10b combine with 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, particularly preferably an alkyl group.

M is for example Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Zr.

As the hydrocarbon group for Q, an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms are preferable. Examples of alkyl groups 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 1,3-trimethylbutyl group and neopentyl group; examples of cycloalkyl groups having 3 to 10 carbon atoms include cyclohexylmethyl group, cyclohexyl group and 1-methyl-1-cyclohexyl group. More preferably, the number of carbon atoms in the hydrocarbon group is 5 or less.

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 Examples include ^4-1,4 -ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis(trimethylsilyl)-1,3-butadiene.

Examples of anionic ligands include alkoxy groups such as a methoxy group and a tert-butoxy group; aryloxy groups such as a phenoxy group; carboxylate groups such as an acetate group and a benzoate group; and sulfonate groups such as a mesylate group and a tosylate group. be.

Neutral ligands capable of coordinating with a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine; tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-dimethoxy Ethers such as ethane are exemplified.

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, more preferably 1; These values of n are preferable from the viewpoint of efficiently synthesizing the polymer.
j is an integer of 1 to 4, preferably 2;

Examples of the bridged metallocene compound represented by formula [A3] include (8-octamethylfluorene-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6 ,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride, or (8-(2,3,6,7-tetramethylfluorene)-12′-yl-(2-(adamantane- 1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride is particularly preferred. Here, the 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.

- Organic aluminum oxy compound (b-1)
Examples of the organoaluminumoxy compound (b-1) include conventionally known aluminoxanes such as compounds represented by the following formula [B1] and compounds represented by the following formula [B2], and structures represented by the following formula [B3]. and a boron-containing organoaluminumoxy compound represented by the following formula [B4].
Compound (b-1) may be used alone or in combination of two or more.

In formulas [B1] and [B2], R is a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, and n is an integer of 2 or more, preferably 3 or more, more preferably 10 or more.
In formulas [B1] and [B2], methylaluminoxane in which R is a methyl group is preferably used.

In formula [B3], Me is a methyl group, R is independently a hydrocarbon group having 2 to 10 carbon atoms, and m and n are each independently an integer of 2 or more.
Modified methylaluminoxanes [B3] can be prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane [B3] is generally called MMAO (modified methylaluminoxane). MMAO can be prepared specifically by the methods mentioned in US Pat. No. 4,960,878 and US Pat. No. 5,041,584.

In addition, modified methylaluminoxane prepared using trimethylaluminum and triisobutylaluminum (that is, R is an isobutyl group in formula [B3]) is also available from Tosoh Finechem Co., Ltd., etc. as commercial products such as MMAO and TMAO. commercially available under the name

MMAO is an aluminoxane with improved solubility in various solvents and improved storage stability.
Specifically, unlike compounds that are insoluble or sparingly soluble in benzene, such as compounds represented by formula [B1] or [B2], MMAO is an aliphatic hydrocarbon, an alicyclic hydrocarbon and an aromatic It dissolves in hydrocarbons.

In formula [B4], R ^c is a hydrocarbon group having 1 to 10 carbon atoms. Each of a plurality of R ^d is independently a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

In the production method using the olefin polymerization catalyst, the polymer can be produced even at a high temperature as described later. Therefore, benzene-insoluble or sparingly soluble organoaluminumoxy compounds such as those exemplified in JP-A-2-78687 can also be used. In addition, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more alkyl groups described in JP-A-2-24701 and JP-A-3-103407, etc. It can be used preferably.

The above-mentioned "benzene-insoluble or sparingly soluble" organoaluminumoxy compound means that the amount dissolved in benzene at 60°C is usually 10% by mass or less, preferably 5% by mass or less, particularly preferably 5% by mass or less, in terms of Al atoms. is 2% by mass or less, and refers to an organoaluminum oxy compound.

- A compound (b-2) that forms an ion pair by reacting with the bridged metallocene compound (A)
As the compound (b-2) (hereinafter also referred to as "ionic compound (b-2)") that reacts with the bridged metallocene compound (A) to form an ion pair, JP-A-1-501950, JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, JP-A-2004-51676, US Patent No. Lewis acids, ionic compounds, borane compounds and carborane compounds described in, for example, No. 5,321,106 are exemplified. Further examples are heteropolycompounds and isopolycompounds. Among these, a compound represented by the following formula [B5] is preferable.
The ionic compound (b-2) may be used singly or in combination of two or more.

In formula [B5], R ^e+ is exemplified by H ⁺ , oxonium cation, carbenium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal. R ^f , R ^g , R ^h and R ⁱ each independently represent an organic group, preferably an aryl group or a halogen-substituted aryl group.

Examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, and tris(dimethylphenyl)carbenium cation.

Ammonium cations include trimethylammonium cations, triethylammonium cations, tri(n-propyl)ammonium cations, triisopropylammonium cations, tri(n-butyl)ammonium cations, trialkylammonium cations such as triisobutylammonium cations; -N,N-dialkylanilinium cations such as dimethylanilinium cation, N,N-diethylanilinium cation, and N,N,2,4,6-pentamethylanilinium cation; diisopropylammonium cation, dicyclohexylammonium cation, etc. Dialkylammonium cations are exemplified.

Phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cations, tris(methylphenyl)phosphonium cations and tris(dimethylphenyl)phosphonium cations.

Of the above examples, R ^e+ is preferably a carbenium cation or an ammonium cation, and particularly preferably a triphenylcarbenium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation.

When R ^{e +} is a carbenium cation, triphenylcarbeniumtetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(3,5-ditrifluoromethylphenyl)borate, tris( Examples include 4-methylphenyl)carbeniumtetrakis(pentafluorophenyl)borate and tris(3,5-dimethylphenyl)carbeniumtetrakis(pentafluorophenyl)borate.

When R ^e+ is an ammonium cation, trialkylammonium salts, N,N-dialkylanilinium salts and dialkylammonium salts are exemplified.

Specific examples of trialkylammonium salts include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis ( o-tolyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(2,4 -dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(4-trifluoromethylphenyl)borate, tri(n-butyl)ammonium tetrakis (3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammonium tetrakis(o-tolyl)borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis(p-tolyl)borate, dioctadecylmethyl ammonium tetrakis(o-tolyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl)borate , dioctadecylmethylammonium tetrakis(4-trifluoromethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-ditrifluoromethylphenyl)borate, and dioctadecylmethylammonium.

Specific examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis (3,5-ditrifluoromethylphenyl)borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(3,5 -ditrifluoromethylphenyl)borate, N,N,2,4,6-pentamethylanilinium tetraphenylborate, and N,N,2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate. be.

Specific examples of dialkylammonium salts include diisopropylammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

- Organoaluminum compound (b-3)
Examples of the organoaluminum compound (b-3) include an organoaluminum compound represented by the following formula [B6], and a complex alkylate of a Group 1 metal of the periodic table and aluminum represented by the following formula [B7]. .
Compound (b-3) may be used alone or in combination of two or more.

R ^am _Al (OR ^b ) _n H _p X _q [B6]
In formula [B6], R ^a and R ^b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is 0<m≦3, n is 0≤n<3, p is 0≤p<3, q is a number satisfying 0≤q<3, and m+n+p+q=3.

Examples of the organoaluminum compound [B6] include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum and trioctylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum; tri-branched alkylaluminum such as tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triphenyl triarylaluminum such _{as aluminum} and tritolylaluminum _; dialkylaluminum hydride _{such as} diisopropylaluminum hydride and _{diisobutylaluminum} hydride _; y and z are positive numbers and z≤2x.) alkenyl aluminum such as isoprenyl aluminum; alkyl aluminum alkoxides such as isobutyl aluminum methoxide and isobutyl aluminum ethoxide; dialkylaluminum alkoxides ^such as _{diethylaluminum} ethoxide _and dibutylaluminum butoxide ^; alkylaluminum sesquialkoxides such as ^{ethylaluminum sesquiethoxide} and butylaluminum sesquibutoxide; is synonymous with R ^a and R ^b in formula [B6].) Partially alkoxylated alkylaluminum having an average composition represented by: diethylaluminum phenoxide, diethylaluminum (2,6-di-tert- butyl-4-methylphenoxide); dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; ethyl aluminum sesquichloride, butyl aluminum sesquichloride, alkylaluminum sesquihalides such as ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dihydride, Partially hydrogenated aluminum alkyls such as alkylaluminum dihydrides such as propylaluminum dihydride; partially alkoxylated and halogenated aluminum alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide. is exemplified.

^{M2AlRa4 [} _B7 ]
In formula [B7], M ² is Li, Na or K, and a plurality of R ^a are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

Examples of the complex alkylated product [B7] include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ . Compounds similar to the complex alkylated product [B7] can also be used, exemplified by organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. ( _C2H5 ) _2AlN ( _{C2H5 )} Al( _C2H5 ) ₂ is exemplified as such _a compound _.

As the organoaluminum compound (b-3), trimethylaluminum and triisobutylaluminum are preferred from the standpoint of easy availability.

・Carrier (C)
A carrier (C) may be used as a component of the olefin polymerization catalyst. The carrier (C) is an inorganic compound or an organic compound, and is a granular or particulate solid.
One type of carrier (C) may be used alone, or two or more types may be used.

Examples of the inorganic compound include porous oxides, inorganic halides, clay minerals, clays (usually composed mainly of clay minerals), ion-exchangeable layered compounds (most clay minerals are ion-exchangeable It is a layered compound.) is exemplified. Examples of porous oxides include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ ; composites or mixtures containing these oxides. . As composites or mixtures, natural or synthetic zeolites, SiO ₂ --MgO, SiO ₂ --Al ₂ O ₃ , SiO ₂ --TiO ₂ , SiO ₂ --V ₂ O ₅ , SiO ₂ --Cr ₂ O ₃ , SiO ₂ -- TiO ₂ --MgO is exemplified. Among these, porous oxides containing either or both of SiO ₂ and Al ₂ O ₃ as main components are preferred.

The properties of the porous oxide vary depending on the type and manufacturing method, but the particle diameter is preferably 10 to 300 μm, more preferably 20 to 200 μm; the specific surface area is preferably 50 to 1000 m ² /g, more preferably is between 100 and 700 m ² /g; the pore volume is preferably between 0.3 and 3.0 cm ³ /g. Such porous oxides are calcined at 100 to 1000° C., preferably 150 to 700° C., if necessary.

Examples of inorganic halides include MgCl ₂ , MgBr ₂ , MnCl ₂ and MnBr ₂ . The inorganic halide may be used as it is, or may be used after pulverizing with a ball mill, vibration mill, or the like. Alternatively, a component obtained by dissolving the inorganic halide in a solvent such as alcohol and then depositing it in the form of fine particles using a precipitating agent can also be used.

Clays, clay minerals, and ion-exchangeable layered compounds are not limited to naturally occurring ones, and artificially synthesized ones can also be used. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with weak bonding force, and the ions contained therein can be exchanged.

Specifically, clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, synthetic mica, montmorillonite group, vermiculite, ryokudite group, palygorskite, Examples include kaolinite, nacrite, dickite, hectorite, teniolite, and halloysite; ion-exchangeable layered compounds include ions having layered crystal structures such as hexagonal close-packed, antimony, _CdCl2 , and _CdI2 types; Crystalline compounds are exemplified. Specifically, the ion-exchange layered compounds include α-Zr(HAsO ₄ ) _{2.H 2} O, α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) _{2.3H 2} O, α- Ti( _HPO4 ) ₂ , α-Ti( _HAsO4 )2.H2O, α-Sn( _HPO4 ) _{2.H2O ,} γ-Zr( _{HPO4 ) 2} , γ _- Ti( _HPO4 ) ₂ , γ-Ti(NH ₄ PO ₄ ) ₂ ·H ₂ O and the like.

It is also preferable to chemically treat clay and clay minerals. Any chemical treatment can be used, such as a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment.

Further, the ion-exchangeable layered compound may be made into a layered compound with expanded interlayer spacing by exchanging the exchangeable ions between the layers with other bulky ions by utilizing its ion-exchangeability. Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars. For example, oxide pillars can be formed between the layers by intercalating the metal hydroxide ions described below between the layers of the layered compound and then dehydrating it by heating. The introduction of another substance between the layers of the layered compound is called intercalation.

Guest compounds for intercalation include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ ( R is a hydrocarbon group, etc.); metal hydroxide ions such as [ _Al13O4 (OH) ₂₄ ] ⁷⁺ , _{[ Zr4} (OH) ₁₄ ] ²⁺ , [ _Fe3O ( _OCOCH3 ) ₆ ] ⁺ are exemplified. These guest compounds may be used alone or in combination of two or more.

Further, when intercalating the guest compound, a metal alkoxide (R is a hydrocarbon group or the like) such as Si(OR) ₄ , Al(OR) ₃ or Ge(OR) ₄ is hydrolyzed and polycondensed. A polymer, colloidal inorganic compound such as SiO ₂ , etc. can also coexist.
Among the inorganic compounds, clay minerals and clays are preferred, with the montmorillonite group, vermiculite, hectorite, taeniolite and synthetic mica being particularly preferred.

Examples of the organic compound include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, (co)polymers synthesized with ethylene and an α-olefin having 3 to 20 carbon atoms as main components; (co)polymers synthesized with vinylcyclohexane and styrene as main components; Modified polymers are exemplified.

・Organic compound component (D)
An organic compound component (D) may be used as a component of the olefin polymerization catalyst. The organic compound component (D) is used, if necessary, for the purpose of improving the polymerization performance in the α-olefin polymerization reaction and the physical properties of the olefin polymer. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.
The organic compound component (D) may be used alone or in combination of two or more.

- Structure of Olefin Polymerization Catalyst When olefin polymerization is carried out using the olefin polymerization catalyst, the amount of each component that can constitute the olefin polymerization catalyst is, for example, as follows.

(1) The bridged metallocene compound (A) is used in such an amount that it is usually 10 ^-9 to 10 ^-1 mol, preferably 10 ^-8 to 10 ^-2 mol, per liter of reaction volume.

(2) When the organoaluminumoxy compound (b-1) is used as a component of the olefin polymerization catalyst, the compound (b-1) is crosslinked with the aluminum atom (Al) in the compound (b-1). It is used in such an amount that the molar ratio [Al/M] to all transition metal atoms (M) in the metallocene compound (A) is usually 0.01-5000, preferably 0.05-2000.

(3) When the ionic compound (b-2) is used as a component of the olefin polymerization catalyst, the compound (b-2) is added to the compound (b-2) and the bridged metallocene compound (A). It is used in such an amount that the molar ratio [(b-2)/M] to the transition metal atom (M) is usually 1-10, preferably 1-5.

(4) When the organoaluminum compound (b-3) is used as a component of the olefin polymerization catalyst, the compound (b-3) is added to the compound (b-3) and the bridged metallocene compound (A). It is used in such an amount that the molar ratio [(b-3)/M] to the transition metal atom (M) is usually 10-5000, preferably 20-2000.

(5) When the organic compound component (D) is used as a component of the olefin polymerization catalyst and the compound (B) is the organoaluminum oxy compound (b-1), the organic compound component (D) and the compound ( In an amount such that the molar ratio [(D)/(b-1)] with b-1) is usually 0.01 to 10, preferably 0.1 to 5; compound (B) is ionic In the case of the compound (b-2), the molar ratio [(D)/(b-2)] between the organic compound component (D) and the compound (b-2) is usually 0.01 to 10, preferably When the compound (B) is an organoaluminum compound (b-3), the molar ratio between the organic compound component (D) and the compound (b-3) [(D) /(b-3)] is usually used in an amount of 0.01 to 2, preferably 0.005 to 1.

-Polymerization method Polymerization in the production of the polymers (A) and (B) can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method.
In the liquid phase polymerization method, an inert hydrocarbon medium may be used. Hydrogen; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane.
The inert hydrocarbon medium may be used singly or in combination of two or more. A so-called bulk polymerization method can also be used in which the liquefied olefin itself, which can be supplied to the polymerization, is used as a solvent.

The polymerization temperature in the polymerization is usually −50 to +200° C., preferably 0 to 180° C.; the polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of a batch system, a semi-continuous system and a continuous system. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions. The molecular weight of the resulting polymer can be adjusted by allowing hydrogen or the like to exist in the polymerization system, by changing the polymerization temperature, or by adjusting the amount of compound (B) used.

The polymerization can produce a polymer having high stereoregularity, a high melting point, and a high molecular weight while maintaining high catalytic activity even under high-temperature conditions that are advantageous in industrial production methods. Under such high temperature conditions, the polymerization temperature is usually 40° C. or higher, preferably 40 to 200° C., more preferably 45 to 150° C., particularly preferably 50 to 150° C. temperature).

Hydrogen, in particular, can be said to be a preferable additive because it has the effect of improving the polymerization activity of the catalyst and the effect of increasing or decreasing the molecular weight of the polymer. When hydrogen is added to the system, the appropriate amount is about 0.00001 to 100 NL per mole of olefin. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system can be adjusted by a method of performing a reaction that produces or consumes hydrogen in the system, a method of separating hydrogen using a membrane, a method of It can also be adjusted by discharging the gas out of the system.

After the polymer obtained by the above polymerization is synthesized by the above method, it may be subjected, if necessary, to post-treatment steps such as a catalyst deactivation treatment step, a catalyst residue removal step, a drying step, and the like.

Further, when the polymers (A) and (B) are graft-modified (co)polymers, a monomer containing an ethylenically unsaturated bond is added to the 4-methyl-1-pentene (co)polymer, an organic peroxide The graft modified product can be produced by graft modification using.

Examples of ethylenically unsaturated bond-containing monomers used for graft modification include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated Carboxylic acid or derivatives thereof, vinyl ester compounds, vinyl chloride, and carbodiimide compounds can be mentioned. Unsaturated carboxylic acids or derivatives thereof are particularly preferred.

The modified amount of the modified product (graft amount of the monomer) is usually 0.1 to 50% by mass, preferably 0.2 to 30% by mass, more preferably 0.2%, when the modified product is 100% by mass. ~10% by mass.

When a modified polymer is used as the polymer (A) or (B), the adhesiveness and compatibility with other resins are excellent, and the surface wettability of the resulting molded article may be improved. Also, by using a modified product, it may sometimes be possible to add compatibility or adhesiveness with materials other than resin (glass, metal, wood, etc.).

Further, when a modified product in which the amount of grafting of the monomer (e.g., unsaturated carboxylic acid and/or derivative thereof) is within the above range, the composition (X) is a polar group-containing resin (e.g., polyester, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyamide, PMMA, polycarbonate, etc.).

<Other ingredients>
The composition (X) may optionally contain a resin additive (hereinafter also referred to as "additive (C)"), depending on its use, to the extent that the effects of the present invention are not impaired. .

<Additive (C)>
Examples of the additive (C) include nucleating agents, antiblocking agents, pigments, dyes, fillers, lubricants, plasticizers, release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, agent, antistatic agent, weather stabilizer, heat stabilizer, anti-slip agent, foaming agent, crystallization aid, anti-fogging agent, anti-aging agent, hydrochloric acid absorber, impact modifier, cross-linking agent, co-cross-linking agent, cross-linking Auxiliaries, adhesives, softeners, processing aids, and dispersants.
Additives (C) may be used alone or in combination of two or more.

The content of the additive (C) is not particularly limited as long as it does not impair the object of the present invention, but the total amount of the additives to be blended is 0.001 to 30% by mass with respect to the total mass of the composition (X). is preferred.

As the nucleating agent, known nucleating agents can be used to further improve the moldability of the composition (X), that is, to raise the crystallization temperature and increase the crystallization rate. Specifically, dibenzylidene sorbitol-based nucleating agent, phosphate ester salt-based nucleating agent, rosin-based nucleating agent, benzoic acid metal salt-based nucleating agent, fluorinated polyethylene, 2,2-methylenebis(4,6-di-t -butylphenyl)sodium phosphate, pimelic acid and its salts, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, ethylene bis stearamide and the like.

The amount of the nucleating agent is not particularly limited, but is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymers (A) and (B). The nucleating agent can be added as appropriate during production of the polymer, after polymerization, or during molding.

A known antiblocking agent can be used as the antiblocking agent. Specifically, finely powdered silica, finely powdered aluminum oxide, finely powdered clay, powdered or liquid silicone resin, tetrafluoroethylene resin, finely powdered crosslinked resin such as crosslinked acrylic, methacrylic resin powder, amide-based lubricant, etc. are mentioned. Among these, finely divided silica and crosslinked acrylic and methacrylic resin powders are preferred.

Pigments include inorganic pigments (eg, titanium oxide, iron oxide, chromium oxide, cadmium sulfide) and organic pigments (eg, azo lake, thioindigo, phthalocyanine, anthraquinone). Examples of dyes include azo dyes, anthraquinone dyes, and triphenylmethane dyes. The amount of these pigments and dyes to be added is not particularly limited, but the total amount is usually 5% by mass or less, preferably 0.1 to 3% by mass, based on the total mass of composition (X).

Examples of 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 Examples include oxides (iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate, etc.) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powders, mica, and glass flakes.

Lubricants include, for example, waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearamide).

Examples of plasticizers include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methyl acetyl ricinoleate, etc.), aliphatic dicarboxylic acid esters (adipic acid-propylene glycol-based polyesters, etc.), aliphatic tricarboxylic acid esters (triethyl citrate, etc.), phosphoric acid triesters (triphenyl phosphate, etc.), epoxy fatty acid esters (epoxybutyl stearate, etc.), and petroleum resins.

Examples of release agents include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4-30) (hydrogenated castor oil, etc.), glycol esters of fatty acids, fluid paraffin.

A known antioxidant can be used as the antioxidant. Specifically, phenol (2,6-di-t-butyl-4-methylphenol etc.), polycyclic phenol (2,2′-methylenebis(4-methyl-6-t-butylphenol etc.), phosphorus system (tri(2,4-di-t-butylphenyl) phosphate, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate, etc.), sulfur system (thiodipropion dilauryl acid, etc.), amine-based antioxidants (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.), inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). ).

Examples of ultraviolet absorbers include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based ultraviolet absorbers.
Antibacterial agents include, for example, quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodine.

Surfactants may include nonionic, anionic, cationic or amphoteric surfactants. Examples of 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; Polyhydric alcohol type nonionic surfactants such as fatty acid esters, pentaerythritol fatty acid esters, sorbit or sorbitan fatty acid esters, alkyl ethers of polyhydric alcohols, and fatty amides of alkanolamine can be used. Examples of anionic surfactants include sulfate ester salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzenesulfonates, alkylsulfonates and paraffinsulfonates, and higher alcohol phosphates. A phosphate ester salt is mentioned. Cationic surfactants include, for example, quaternary ammonium salts such as alkyltrimethylammonium salts. Amphoteric surfactants include, for example, amino acid-type double-faced surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkylhydroxyethylbetaines.

Antistatic agents include, for example, the aforementioned surfactants, fatty acid esters, and polymeric antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymeric antistatic agents include polyether ester amides.

Examples of heat-resistant stabilizers include conventionally known stabilizers such as amine-based stabilizers, phenol-based stabilizers, and sulfur-based stabilizers. Specifically, aromatic secondary amine-based stabilizers such as phenylbutylamine and N,N'-di-2-naphthyl-p-phenylenediamine; Phenolic stabilizers such as butyl-4-hydroxy)hydrocinnamate]methane, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; bis[2-methyl-4-(3- thioether-based stabilizers such as n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate-based stabilizers such as nickel dibutyldithiocarbamate; 2-mercaptobenzilimidazole and zinc salts of 2-mercaptobenzimidazole; sulfur stabilizers such as dilauryl thiodipropionate and distearyl thiodipropionate; These stabilizers may be used singly or in combination of two or more.

As a cross-linking agent, for example, an organic peroxide is used.
Examples of organic peroxides include dicumyl organic peroxide, di-tert-butyl organic peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di -(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl- 4,4-bis(tert-butylperoxy)valerate, benzoyl organic peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl organic peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate , diacetyl organic peroxide, lauroyl organic peroxide, tert-butyl cumyl organic peroxide.

The organic peroxide is preferably used in a proportion of 0.05 to 10 parts by weight per 100 parts by weight of the total amount of the polymers (A) and (B).

In the cross-linking treatment with an organic peroxide, sulfur, p-quinonedioxime, p,p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, tri Peroxy cross-linking coagents such as methylolpropane-N,N'-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl Multifunctional methacrylate monomers such as methacrylates, and multifunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be incorporated.

A uniform and moderate cross-linking reaction can be expected by using the above compound. Among these, divinylbenzene is particularly preferably used. Divinylbenzene is easy to handle, has good compatibility with the polymers (A) and (B), has an action of solubilizing organic peroxides, and functions as a dispersant for organic peroxides. For this reason, a homogeneous cross-linking effect is obtained, and a dynamically heat-treated product with well-balanced fluidity and physical properties can be obtained.

The cross-linking aid is preferably used in a proportion of 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the polymers (A) and (B).

Softening agents include, for example, process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, mineral oil softening agents such as vaseline, coal tar softening agents such as coal tar and coal tar pitch, castor oil, rapeseed oil, Fatty oil-based softeners such as soybean oil and coconut oil, waxes such as tall oil, bees wax, carnauba wax and lanolin, fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate and calcium stearate or metal salts thereof, Naphthenic acid or its metallic soap, pine oil, rosin or its derivatives, terpene resin, petroleum resin, coumarone-indene resin, synthetic high-molecular substances such as atactic polypropylene, ester-based plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate, etc. carbonic acid ester plasticizer such as diisododecyl carbonate, microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, and hydrocarbon synthetic lubricating oil. Among these, petroleum-based softeners and hydrocarbon-based synthetic lubricating oils are preferred.

Although the amount of the softening agent is not particularly limited, it is preferably in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymers (A) and (B). The softener facilitates processing and helps disperse carbon black and the like when preparing composition (X).

<Method for producing composition (X)>
The method for producing the composition (X) is not particularly limited, but for example, the polymers (A), (B), and, if necessary, other optional components are mixed in the above addition ratio, and then melt-kneaded. can be obtained with

The melt-kneading method is not particularly limited, and can be carried out using a melt-kneading device such as an extruder that is generally commercially available.
For example, the cylinder temperature of the portion where kneading is performed by the kneader is usually 240 to 320°C, preferably 270 to 300°C. If the temperature is lower than 240° C., kneading becomes insufficient due to insufficient melting, and it may be difficult to improve the physical properties of the composition. On the other hand, if the temperature is higher than 320°C, thermal decomposition of components such as polymers (A) and (B) may occur.

≪Molded body≫
The molded article according to the present invention is not particularly limited as long as it contains the composition (X), but is usually obtained by molding the composition (X).

As a method for molding the composition (X), various known molding methods can be applied, for example, injection molding, extrusion molding, injection stretch blow molding method, blow molding method, cast molding method, calendar molding method, press molding, Various molding methods such as stamping molding, inflation molding, and roll molding can be used. These molding methods can be processed into desired molded articles such as films, sheets, hollow molded articles, injection molded articles, fibers and the like. The molding conditions are the same as those for conventionally known 4-methyl-1-pentene polymers. There are no particular restrictions on the shape of the molded body. For example, it may be tube-shaped, film-shaped, sheet-shaped, membrane-shaped, tape-shaped, plate-shaped, rod-shaped, fiber-shaped, or non-woven fabric-shaped.

The composition (X) and the molded article can be used without restriction for applications in which conventional 4-methyl-1-pentene polymers have been used, but the impact resistance, rigidity, heat resistance and transparency is more suitable for applications requiring
Specific uses include, for example, containers, films, and packaging materials.

Examples of containers include tableware, food containers, seasoning containers, kitchen utensils, retort containers, freezer storage containers, retort pouches, microwave heat-resistant containers, microwave steam sterilization containers, frozen food containers, frozen dessert cups, cups, Baby products (e.g. baby bottles), bottle containers, medical instruments (e.g. blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottles), medicines Containers, detergent containers, softener containers, bleach containers, shampoo containers, conditioner containers, cosmetic containers, perfume containers, toner containers, powder containers, adhesive containers, gasoline tank containers, kerosene containers, heat resistant Examples include containers, animal cages, and laboratory equipment (eg, physics and chemistry laboratory equipment).

Applications of films include, for example, packaging materials for foods (e.g., meat, processed fish, vegetables, fruits, fermented foods, retort foods, confectionery, medicine, bulbs, seeds, mushrooms), wrap films, cell culture bags, Cell test films, heat-resistant vacuum-formed containers, containers for prepared dishes, lids for prepared dishes, baking cartons, various release films, and the like.

Films further include, for example, release films for flexible printed circuit boards, release films for ACM substrates, release films for rigid substrates, release films for rigid flexible substrates, release films for advanced composite materials, and carbon fiber composite materials. Release film for curing, Release film for curing glass fiber composite material, Release film for curing aramid fiber composite material, Release film for curing nanocomposite material, Release film for curing filler filler, Release film for semiconductor encapsulation Films, release films for polarizing plates, release films for diffusion sheets, release films for prism sheets, release films for reflection sheets, cushion films for release films, release films for fuel cells, release films for various rubber sheets Release films such as films, release films for urethane curing, release films for epoxy curing, solar cell encapsulant sheets, solar cell back sheets, plastic films for solar cells, battery separators, separators for lithium-ion batteries, fuel Battery electrolyte membrane, adhesive/adhesive material separator, light guide plate, optical disk, dicing tape, back grinding tape, die bonding film, double-layer FCCL, film capacitor film, etc. Semiconductor process film base material, adhesive material, separator, Adhesive film, stress relaxation film, pellicle film, polarizing plate film, polarizing plate protective film, liquid panel protective film, optical component protective film, lens protective film, electrical component/electronic product protective film, mobile phone Phone protective film, PC protective film, Touch panel protective film, Window glass protective film, Baking finish film, Masking film, Capacitor film, Capacitor film, Tab lead film, Capacitor film for fuel cells, Reflective film, Diffusion film, Laminates (including glass), radiation-resistant films, γ-ray-resistant films, protective films such as porous films, heat-dissipating films and sheets, molds for manufacturing electronic component seals, LED molds, laminates for high-frequency circuits, high-frequency cables optical waveguide substrates, glass fiber composites, carbon fiber composites, glass interlayer films, films for laminated glass, window films for building materials, arcade domes, gymnasium window glass alternatives, films for LCD substrates, bulletproof materials, bulletproof glass film, heat shield sheet, heat shield film, release liner for synthetic leather, release liner for advanced composite materials, release liner for curing carbon fiber composite materials, release liner for curing glass fiber composite materials, release liner for curing aramid fiber composite materials , release paper for curing nanocomposite materials, release paper for curing filler fillers, etc., heat and water resistant photographic paper, packaging film, release film, breathable film, reflective film, synthetic paper, display film, display conductive films and display barrier films.

Examples of packaging materials include food packaging materials (e.g., meat packaging materials, processed fish packaging materials, vegetable packaging materials, fruit packaging materials, fermented food packaging materials, confectionery packaging materials, oxygen absorbent packaging materials, retort food packaging materials ), freshness-preserving films, medical packaging materials, pharmaceutical packaging materials, cell culture bags, cell inspection films, bulb packaging materials, seed packaging materials, vegetable and mushroom cultivation films, heat-resistant vacuum-formed containers, prepared dish containers, lid materials for prepared dishes , industrial wrap film, household wrap film, and baking cartons.

Other uses include mandrels for manufacturing rubber hoses, sheaths, sheaths for manufacturing rubber hoses, hoses, tubes, release paper for synthetic leather, medical tubes, industrial tubes, cooling water piping, hot water piping, wire coating materials, Wave signal cable covering material, high-frequency signal cable covering material, eco-friendly electric wire covering material, vehicle-mounted cable covering material, signal cable covering material, high-voltage electric wire insulator, wiring duct, cosmetic/perfume spray tube, medical tube, infusion tube, Pipes, wire harnesses, interior and exterior materials for automobiles, motorcycles, railway vehicles, aircraft, ships, etc., wear-resistant interior and exterior materials for automobiles, instrument panel skins, door trim skins, rear package trim skins, ceiling skins, rear pillar skins, seats Back garnish, console box, armrest, airbag case lid, shift knob, assist grip, side step mat, meter cover, battery cap, fuse, automatic flushing sensor parts, ignition, coil bobbin, bushing, bumper, car heater fan, radiator grill, Wheel caps, EV power connectors, automotive display polarizers, louvers, armrests, rail insulation plates, motorcycle windbreaks, reclining covers, trunk seats, seat belt buckles, inner and outer moldings, bumper moldings, side moldings, roof moldings, Molding materials such as belt moldings, automotive sealing materials such as air spoilers, door seals, body seals, glass run channels, mud guards, kicking plates, step mats, license plate housings, automotive hose members, air duct hoses, air duct covers, Air intake pipe, air dam skirt, timing belt cover seal, bonnet cushion, door cushion, cup holder, side brake grip, shift knob cover, seat adjustment knob, wire harness grommet, suspension cover boot, glass guide, inner belt line seal, roof guide , trunk lid seals, molded quarter window gaskets, corner moldings, glass encapsulations, hood seals, glass run channels, secondary seals, bumper parts, body panels, side shields, door skins, weather strip materials, hoses, steering wheels , wire harness covers, seat adjuster covers and other automobile interior and exterior materials, damping tires, static and dynamic tires, car racing tires, special tires such as radio-controlled tires, packing, automobile dust covers, lamp seals, automobile boot materials, rack and Pinion boots, timing belts, wire harnesses, grommets, emblems, air filter packings, automotive connectors, ignition coils, switches, lamp reflectors, relays, electric control unit cases, sensor housings, headlamps, meter plates, bearing retainers, thrust washers , lamp reflectors, door handles, glazing, panorama roofs, solenoid valves, ECU cases, unit connection connectors, alternators, HEV terminal blocks, solenoid valves, coil sealing parts, surface materials for furniture, footwear, clothing, bags, building materials, etc. , construction sealing materials, waterproof sheets, building material sheets, pipe joints, dressers, bathroom ceilings, impellers, building gaskets, window films for building materials, iron core protection materials, soil improvement sheets, waterproof materials, joint materials, gaskets, Doors, door frames, window frames, rims, baseboards, opening frames, etc., flooring materials, ceiling materials, wallpapers, health products (e.g. non-slip mats/sheets, fall prevention films/mats/sheets), health equipment components, Shock-absorbing pads, protectors/protective equipment (e.g. helmets, guards), sporting goods (e.g. sports grips, protectors), sports protective gear, rackets, mouth guards, balls, golf balls, transport equipment (e.g. transport shocks) Absorbing grips, shock absorbing sheets), damping pallets, shock absorbing dampers, insulators, shock absorbing materials for footwear, shock absorbing foams, shock absorbing materials such as shock absorbing films and sheets, grip materials (writing instruments, tools, sports equipment, Vehicle handles, daily necessities, electrical appliances, furniture, etc.), camera bodies, camera parts, OA equipment parts, copier structural parts, printer structural parts, aircraft parts, in-flight meal trays, facsimile structural parts, pump parts, electric tools Parts, Dryer washing machine parts, Heater pump spout/outlet, IH rice cooker, Rice cooker inner lid, Range roller stay ring, Vacuum cleaner fan guide, Electronic jar pump/filter case, Garbage disposer parts/Treatment tank・Heat drying parts, milk meters, filter bowls, escalator parts, ultrasonic motor housings, absolute encoders, small pump housings, TV parts, hair dryer housings, lighting covers, miscellaneous goods, coffee drippers, humidifier parts, iron parts, water equipment Parts, water bottles, combs, fountain pens, pencil cases, pencil sharpeners, sports and leisure goods, ski goggles, karate and kendo armor, surfing fins, musical instruments, fish tanks, sandals, snow shovels, fishing rod cases, toys, shoe soles, shoe soles , Shoe midsoles, inner soles, soles, sandals, chair covers, bags, school bags, clothing such as jackets and coats, obis, sticks, ribbons, notebook covers, book covers, key chains, pen cases, wallets, chopsticks, lotus, Microwave cooking pot, business card holder, commuter pass holder, suction cup, toothbrush, flooring, gymnastics mat, electric tool member, farm equipment member, heat dissipation material, transparent substrate, soundproofing material, sound absorbing material, cushioning material, electrical cable, shape memory material , connectors, switches, plugs, home appliance parts (motor parts, housings, etc.), medical gaskets, speaker diaphragms, medical caps, drug stoppers, gaskets, baby food, dairy products, pharmaceuticals, sterilized water, etc. , boiling, high-pressure steam sterilization and other high-temperature processing packing materials, industrial sealing materials, industrial sewing machine tables, license plate housings, cap liners such as PET bottle cap liners, protective film adhesive layers, hot-melt adhesive materials, etc. stationery, office supplies, OA printer legs, FAX legs, sewing machine legs, motor support mats, support members for precision equipment and OA equipment such as audio vibration-proof materials, heat-resistant packing for OA, animal cages, beakers, graduated cylinders, etc. laboratory equipment, medical films and sheets, cell culture films and sheets, syringes, optical media such as CD/DVD/Blu-ray, optical measurement cells, clothing cases, clear cases, clear files, clear sheets, desk mats, artificial Cardiopulmonary, syringe, three-way stopcock, infusion set, surgeon's instrument, flow meter, dental instrument, contact lens sterilizing instrument, inhalation mask, analytical cell, milking machine, fire alarm, fire extinguisher, helmet, safety glasses, IC carriers, pickup lenses, and burn-in sockets are listed.

The composition (X) and the molded article can also be used as fibers.
Applications as fibers include monofilaments, multifilaments, cut fibers, hollow fibers, nonwoven fabrics, elastic nonwoven fabrics, fibers, waterproof fabrics, breathable fabrics and fabrics, paper diapers, sanitary products, sanitary products, filters, bag filters, etc. Filters for dust collection, air cleaners, hollow fiber filters, water purification filters, cloth, paper, gas separation membranes, artificial livers (cases, hollow fibers), reverse osmosis membrane filters.

In addition, the composition (X) and the molded article can be used as a coating material, a film obtained by coating, a sheet, a release material, a water imaging material, an insulating film, an adhesive, an adhesive material, a coated paper, a transparent sealant, a sealant, a hot It is also suitably used for melt-type adhesives, solvent-type adhesives, film-type adhesives, cloth tapes, craft tapes, elastic adhesives, and the like.

Composition (X) can also be processed into fine powder by pulverization. The resulting fine powder can be used, for example, as an additive for ink compositions and coating compositions, as an additive for metallurgical powder compositions, as an additive for ceramic sintering powder compositions, as an additive for adhesives, It can be used as a rubber additive, a toner release agent, a mold release agent, and the like. Furthermore, the obtained fine powder is used as a resin additive for parts for shafts, gears, cams, electric parts, camera parts, automobile parts, household goods, waxes, greases, engine oils, fine ceramics, plating, etc. can also be used as a resin additive.

The present invention will be described in detail based on examples, but the present invention is not limited to these examples.

[Production Example 1] 4-methyl-1-pentene/1-decene copolymer (A1)
In Comparative Example 7 of International Publication No. WO 2006/054613, the content of structural units derived from 4-methyl-1-pentene and 1-decene of the obtained copolymer is as shown in Table 1 below. In addition, a 4-methyl-1-pentene/1-decene copolymer (A1) was obtained by changing the charging amount of the monomers.

[Production Example 2] 4-methyl-1-pentene/1-hexadecene/1-octadecene copolymer (A2)
According to Synthesis Example 4 of WO 2014/050817, (8-octamethylfluorene-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6, 7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride (hereinafter also referred to as “metallocene compound (a)”) was synthesized.

A magnetic stirrer was placed in a sufficiently dried and nitrogen-substituted Schlenk tube, 5.0 μmol of the metallocene compound (a) was added, and 300 eq/cat. of modified methylaluminoxane suspension was added. (n-hexane solvent, 1.50 mmol in terms of aluminum atom) was added with stirring at room temperature, and heptane was added in an amount such that the concentration of the metallocene compound (a) was 1 μmol/mL to prepare a catalyst solution.

In a sufficiently dried, nitrogen-substituted SUS autoclave with an internal volume of 1,500 ml, 4-methyl-1-pentene 500 mL, cyclohexane 250 mL, Linearene 168 (manufactured by Idemitsu Kosan Co., Ltd.) (1-hexadecene and 1-octadecene 1.7 mL of the mixture) and 0.5 mmol of a hexane solution of triisobutylaluminum (Al concentration: 0.5 M) were charged, and after adding 124.3 mL of hydrogen, the polymerization temperature was 60 while stirring at 850 rpm. °C.

0.1 mL of the catalyst solution (concentration of metallocene compound (a): 0.1 μmol) was charged into the autoclave to initiate polymerization, and 20 minutes after the initiation of polymerization, methanol was added to terminate the polymerization.

The polymerization liquid taken out from the cooled/depressurized autoclave was put into a 1:1 solution of acetone and methanol to precipitate the polymer, which was collected by filtration. Thereafter, the recovered polymer was dried under reduced pressure at 80° C. for 12 hours to obtain a 4-methyl-1-pentene/1-hexadecene/1-octadecene copolymer (A2).

[Production Examples 3 to 12] 4-methyl-1-pentene/1-hexadecene/1-octadecene copolymers (A3 to A6 and B1 to B6)
The charged amount of 4-methyl-1-pentene and linearene 168 was changed so that the content of structural units derived from 1-hexadecene and 1-octadecene was the numerical value shown in Table 1 or 2, and hydrogen was added. 4-Methyl-1-pentene/1-hexadecene/1-octadecene copolymers (A3) to (A6) and (B1) to (B6) were prepared in the same manner as in Production Example 2, except that the charging amount was changed. got

<Composition measurement of copolymer>
The content of the structural unit derived from each monomer in the copolymer obtained in the Production Example was calculated from ¹³ C-NMR spectrum using the following apparatus and conditions.

An AVANCE III cryo-500 type nuclear magnetic resonance apparatus manufactured by Bruker was used as an apparatus, o-dichlorobenzene/benzene-d ₆ (4/1 v/v) mixed solvent was used as a solvent, and the sample concentration was 55 mg/0. 6 mL, measurement temperature: 120° C., observation nucleus: ¹³ C (125 MHz), sequence: single-pulse proton broadband decoupling, pulse width: 5.0 μs (45° pulse), repetition time: 5.5 seconds, number of integrations: Under the condition of 64 times, the benzene-d ₆ peak at 128 ppm was measured as a chemical shift reference value. Using the integrated value of the main chain methine signal, the content (mol%) of the structural unit derived from each monomer was calculated. Results are shown in Table 1 or 2.
In these tables, the content of structural units derived from 4-methyl-1-pentene is referred to as 4-methyl-1-pentene content, and derived from a monomer (comonomer) other than 4-methyl-1-pentene. The sum of the contents of the structural units obtained is called the comonomer content.

<Intrinsic viscosity [η] measurement>
The intrinsic viscosity [η] was measured at 135°C using decalin solvent. Specifically, about 20 mg of each copolymer was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135°C. 5 ml of the decalin solvent was added to the decalin solution to dilute it, and then the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated twice, and the value of ηsp/C (dl/g) when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[η] of the copolymers obtained in Production Examples 1 to 6 was set to [η _A ], and [η] of the copolymers obtained in Production Examples 7 to 12 was set to [η _B ]. Results are shown in Table 1 or 2.
[η]=lim(ηsp/C) (C→0)

[Examples 1 to 4 and Comparative Examples 1 to 4]
Each copolymer obtained in the above production example was extruded into a twin-screw extruder (PCM43, manufactured by Ikegai Co., Ltd., screw diameter: 43 mm, temperature: 280°C, A polymer composition was obtained by melt-kneading using a rotating speed of 200 rpm.

The resulting polymer composition was molded into a 0.5 mm thick, Injection specimens were prepared by injecting square plates of 2 mm, 3 mm or 1/4 inch.
Using this injection test piece, the following tests were carried out.

<Melting point (Tm)>
Exothermic and endothermic curves were determined using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., and the temperature at the maximum melting peak position during heating was defined as the melting point (Tm). Measurement was performed as follows.
About 5 mg of a sample was cut out from an injection test piece with a thickness of 0.5 mm, placed in an aluminum pan for measurement, heated from 20° C. to 280° C. at a heating rate of 10° C./min, held at 280° C. for 5 minutes, and then heated to 10° C. After the temperature was lowered to 20°C at a cooling rate of °C/min and held at 20°C for 5 minutes, the temperature was again raised from 20°C to 280°C at a heating rate of 10°C/min, and again at a cooling rate of 50°C/min. The temperature was lowered to 50°C. The melting peak that appeared during the second heating was taken as the melting point (Tm).

<Tensile test>
A 2 mm thick injection test piece was used to prepare an ASTM-4 dumbbell-shaped test piece in accordance with ASTM D638, and a universal tensile tester 3380 manufactured by Instron Co., Ltd. Tensile speed: 50 mm / min, measurement temperature : A tensile test was performed at 23°C to measure the tensile modulus (YM).

<High-speed surface impact test>
Using a 2mm-thick injection test piece, the test piece is clamped using a high-speed puncture impact tester "Hydroshot HITS-P10" (manufactured by Shimadzu Corporation) in accordance with JIS K 7211. At a fixed temperature of 23° C., a striking core with a diameter of 1/2 inch was dropped at the center of the test piece at a falling speed of 3 m/sec to give an impact. The breaking energy when the test piece breaks was determined.

<Izod impact test>
Using a 3 mm thick injection test piece, in accordance with ASTM D256, using a digital impact tester DG-IB type manufactured by Toyo Seiki Seisakusho Co., Ltd., hammer capacity 3.92 J, miss swing accuracy 148.9 °, An Izod impact test was performed at a test temperature of 23° C. to measure the Izod impact strength.

<Load deflection temperature test>
Using an injection test piece with a thickness of 1/4 inch, in accordance with ASTM D648, using an HDT measurement device manufactured by Yasuda Seiki Seisakusho Co., Ltd., heating rate: 50 ° C. per hour, test load: 0.45 MPa A load deflection temperature test was performed under the conditions of , and the load deflection temperature (HDT) was measured.

<Vicat softening temperature test>
Using an injection test piece of 3 mm thickness, in accordance with ASTM D1525, using an HDT measurement device manufactured by Yasuda Seiki Seisakusho Co., Ltd., in silicone oil, heating rate: 50 ° C. per hour, test load: 10 N A Vicat softening temperature test was performed under the conditions to measure the Vicat softening temperature.

<Total light transmittance>
Using a 2mm-thick injection test piece, in accordance with JIS K 7361, a haze/transmittance meter HM-150 (D65 light source) manufactured by Murakami Color Research Laboratory Co., Ltd. was used to measure the total amount of transmitted light. , the total light transmittance was determined by the following formula.
Total light transmittance (%) = 100 × (total transmitted light amount) / (incident light amount)

[Morphology Observation]
A core portion (inside) of a 2 mm-thick injection test piece was thinly shaved and observed with a transmission electron microscope manufactured by JEOL Ltd. 100 island phases with a sea-island structure were observed, and the dispersion diameter was obtained by adding the longest diameter and the shortest diameter of each of the top 10 island phases with the largest areas and averaging them. Specifically, it was calculated by the following formula.
Dispersion diameter (μm) = (total of 10 longest diameters (μm) + 10 shortest diameters total (μm))/20

Claims (3)

70.0 to 85.0% by mass of a 4-methyl-1-pentene (co)polymer (A) that satisfies the following requirement (Aa);
30.0 to 15.0% by mass of 4-methyl-1-pentene copolymer (B) that satisfies the following requirements (Ba) (provided that (co)polymer (A) and copolymer (B) The total is 100% by mass) and
A polymer composition (X) that satisfies the following requirements (X-1) and (X-2) , comprising:
Requirement (Aa): The content of structural units derived from 4-methyl-1-pentene is 96.0 to 100 mol%, and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1 -The content of structural units derived from olefins selected from the group consisting of 4.0 to 0 mol% Requirement (Ba): of structural units derived from 4-methyl-1-pentene The content is 85.0 mol% or more and less than 96.0 mol%, and the content of structural units derived from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 4 more than 0 mol % and 15.0 mol % or less Requirement (X-1): The intrinsic viscosity of each of the (co)polymer (A) and copolymer (B) measured in decalin at 135 ° C. [η _A ] and [η _B ] satisfy the following formula 1.5≦1/[η _A ]×([η _B ]/[η _A ]) ^0.84 ≦5.3
Requirement (X-2): A 2 mm-thick molded article of the polymer composition (X) has a sea-island structure, and 100 island phases of the sea-island structure are observed, and the top 10 island phases with the largest area are identified. The dispersion diameter is 0.3 to 3.0 μm when the value obtained by adding the longest diameter and the shortest diameter and averaging them is taken as the dispersion diameter. The polymer composition (X) according to claim 1 , which satisfies at least one of the following requirements (X-3) to (X-6).
Requirement (X-3): Using a molded body of composition (X) with a thickness of 2 mm, the high-speed surface impact strength at 23 ° C. measured in accordance with JIS K 7211 is 4 to 20 J. Requirement (X-4): Using a molded body of composition (X) with a thickness of 3 mm, it does not break when subjected to an Izod impact test at 23 ° C. in accordance with ASTM D256 Requirement (X-5): Molding of composition (X) with a thickness of 2 mm Using a body, the total light transmittance measured in accordance with JIS K 7361 is 90 to 98.0% Requirement (X-6): Using a 2 mm thick molded body of composition (X), ASTM D638 The tensile modulus measured according to the standard is 1000 to 2000 MPa A molded article comprising the polymer composition (X) according to claim 1 or 2 .