JP2020158681A - Polymer composition comprising 4-methyl-1-pentene-based polymer and molded product - Google Patents

Abstract

To provide a polymer composition and a molded product having excellent balance among heat resistance, rigidity, transparency and impact resistance.SOLUTION: There is provided a polymer composition (X) satisfying (X-1) which comprises 70.0 to 85.0 mass% of a 4-methyl-1-pentene (co)polymer (A) satisfying (A-a), 30.0 to 15.0 mass% of a 4-methyl-1-pentene copolymer (B) satisfying (B-a) (the total of (A) and (B) is 100 mass%). (A-a): the content of a constitutional unit (U1) derived from 4-methyl-1-pentene is 96.0 to 100 mol% and the content of a constitutional 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%, (B-a); the content of the constitutional unit (U1) is 85.0 mol% or more and less than 96.0 mol% and the content of the constitutional unit (U2) is more than 4.0 mol% and 15.0 mol% or less, (X-1): each intrinsic viscosity [ηA] and [ηB] of (A) and (B) measured in decalin at 135°C satisfies the following expression: 0.7≤1/[ηA]×([ηA]/[ηB])0.84≤5.3.SELECTED DRAWING: None

Description

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

4-Methyl-1-pentene-based polymers obtained by copolymerizing 4-methyl-1-pentene with α-olefins such as 1-butene, 1-pentene, and 1-hexene are medical instruments and packaging materials for medical use. , Experimental equipment, cosmetic containers, etc. are widely used. Various 4-methyl-1-pentene polymers have been studied so far (see Patent Documents 1 to 3).

International Publication No. 2005/121192 Japanese Unexamined Patent Publication No. 2008-14145 JP-A-2018-162408

The molded product formed by using the 4-methyl-1-pentene polymer may not have sufficient impact resistance, and it is required to improve the impact resistance. Further, in various applications in which a 4-methyl-1-pentene polymer is used, the molded product is 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, and in particular, impact resistance. In that respect, there was 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 product having an excellent balance of heat resistance, rigidity, transparency and impact resistance.

As a result of diligent studies on a method for solving the above-mentioned problems, it was found that the above-mentioned problems can be solved according to a specific composition, and the present invention has been completed.
A configuration example of the present invention is as follows.

[1] 4-Methyl-1-pentene (co) polymer (A) 70.0 to 85.0% by mass satisfying the following requirement (Aa).
4-Methyl-1-pentene copolymer (B) 30.0 to 15.0% by mass (provided that the (co) polymer (A) and the copolymer (B) satisfy the following requirements (BA). The total is 100% by mass),
A polymer composition (X) that satisfies the following requirements (X-1).
Requirement (A-a): The content of the structural unit derived from 4-methyl-1-pentene is 96.0 to 100 mol%, ethylene and α-olefin having 3 to 20 carbon atoms (4-methyl-1). The content of the structural unit derived from olefin selected from the group consisting of −pentene) is 4.0 to 0 mol% Requirement (BA): Constituent unit derived from 4-methyl-1-pentene The content is 85.0 mol% or more and less than 96.0 mol%, and the content of the structural unit derived from ethylene and α-olefin (excluding 4-methyl-1-pentene) having 3 to 20 carbon atoms is 4. Requirement (X-1) of more than 0.0 mol% and 15.0 mol% or less: Extreme viscosity of each of the (co) polymer (A) and the copolymer (B) measured in decalin at 135 ° C. [Η _A ] and [η _B ] satisfy the following equation 0.7 ≦ 1 / [η _A ] × ([η _A ] / [η _B ]) ^0.84 ≦ 5.3

[2] The polymer composition (X) according to [1], which satisfies the following requirement (X-2).
Requirement (X-2): When observing 100 island fauna with a sea-island structure and adding the longest diameter and the shortest diameter of each of the top 10 island fauna with a large area and averaging them, the value is used as the dispersion diameter. The 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): The high-speed surface impact strength at 23 ° C. measured according to JIS K 7211 using a molded product of the composition (X) having a thickness of 2 mm is 4 to 20 J. Requirement (X-4): Requirement (X-5): Molding of composition (X) with a thickness of 2 mm using a molded product of composition (X) with a thickness of 3 mm and not being destroyed when an Izod impact test at 23 ° C. is performed in accordance with ASTM D256. Total light transmittance measured according to JIS K 7361 using a body is 90 to 98.0% Requirement (X-6): Using a molded product of a composition (X) having a thickness of 2 mm, in ASTM D638. The tensile modulus measured in accordance with this is 1000 to 2000 MPa.

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

According to the present invention, a polymer composition having a good balance of heat resistance, rigidity, transparency and impact resistance without impairing the heat resistance, rigidity and transparency of the 4-methyl-1-pentene polymer and A molded body can be provided.

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

The content of the polymer (A) in the composition (X) is 70.0 to 85.0% by mass, preferably 70.0% by mass, based on 100% by mass of the total of the polymers (A) and (B). It is ~ 80.0% by mass, more preferably 72.0-77.0% by mass.
The content of the polymer (B) in the composition (X) is 30.0 to 15.0% by mass, preferably 30.0% by mass, based on 100% by mass of the total of the polymers (A) and (B). It is ~ 20.0% by mass, more preferably 28.0 to 23.0% by mass.
When the contents of the polymers (A) and (B) are in 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) A composition and a molded product satisfying the above conditions can be easily obtained.
When the content of the polymer (A) is lower than the above range, the heat resistance, rigidity and transparency tend to decrease, and when 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 product in which the physical properties of the 4-methyl-1-pentene polymer are sufficiently exhibited. it can.

The composition (X) is not particularly limited as long as it satisfies the following requirements (X-1), but it is preferable that at least one of the following requirements (X-2) to (X-8) is satisfied, and in particular, all of them are satisfied. It is preferable to meet the requirements of.

[Requirements (X-1)]
The requirement (X-1) is that the ultimate viscosities [η _A ] and [η _B ] of the (co) polymer (A) and the copolymer (B) measured in decalin at 135 ° C. are as follows. Satisfy. Specifically, the ultimate viscosity can be measured by the method described in the following Examples.
0.7 ≤ 1 / [η _A ] x ([η _A ] / [η _B ]) ^0.84 ≤ 5.3

The left side of the equation is preferably 1.0, more preferably 1.5, and the right side of the equation is preferably 5.0, more preferably 4.5.
The above formula is a formula based on Wu's formula regarding the size of islands having a sea-island structure, and by satisfying this formula, a composition or a molded product having particularly excellent impact resistance can be easily obtained. That is, by controlling the [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)]
The requirement (X-2) is that when 100 island fauna with a sea-island structure are observed and the value obtained by adding and averaging the longest diameter and the shortest diameter of each of the top 10 island fauna with a large area is used as the dispersion diameter. It is specified that the dispersion diameter is 0.3 to 3.0 μm. Specifically, the size (diameter) of the island phase can be measured by the method described in the following Examples.
Specifically, the dispersion diameter is calculated by the formula "(total of 10 longest diameters (μm) + total of 10 shortest diameters (μm)) / 20".
The dispersion diameter is preferably 0.3 to 2.8 μm, more preferably 0.4 to 2.6 μm.
When the dispersion diameter is in the above range, that is, the island size is in the above range, a composition or a molded product having particularly excellent impact resistance can be easily obtained.

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

[Requirements (X-4)]
Requirement (X-4) stipulates that a molded product of the composition (X) having a thickness of 3 mm is used and is not broken when subjected to an Izod impact test at 23 ° C. in accordance with ASTM D256. The Izod impact test can be specifically measured by the method described in the following Examples.
The fact that the test piece is not destroyed when the Izod impact test is performed means that the test piece is excellent in impact resistance.

[Requirements (X-5)]
The requirement (X-5) stipulates that a molded product of the composition (X) having a thickness of 2 mm is used and the total light transmittance measured according to JIS K 7361 is 90 to 98.0%. Specifically, the total light transmittance can be measured by the method described in the following Examples.
The total light transmittance is preferably 90.0 to 95.0%, more preferably 90.0 to 93.5%.
It can be said that the fact that the total light transmittance is in the above range does not impair the transparency of the 4-methyl-1-pentene polymer and is excellent in transparency.

[Requirements (X-6)]
The requirement (X-6) stipulates that a molded product of the composition (X) having a thickness of 2 mm is used and the tensile modulus measured according to ASTM D638 is 1000 to 2000 MPa. Specifically, the tensile elastic modulus can be measured by the method described in the following Examples.
The tensile elastic modulus is preferably 1200 to 1700 MPa, more preferably 1300 to 1500 MPa.
It can be said that the tensile elastic modulus in the above range does not impair the rigidity of the 4-methyl-1-pentene polymer and is excellent in rigidity.

[Requirements (X-7)]
Requirement (X-7) specifies that a molded product of the composition (X) having a thickness of 1/4 inch is used and the deflection temperature under load measured according to ASTM D648 is 80 ° C. or higher. Specifically, the deflection temperature under load can be measured by the method described in the following Examples.
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, for example, 110 ° C.
It can be said that the fact that the deflection temperature under load is within the above range does not impair the heat resistance of the 4-methyl-1-pentene polymer and is excellent in heat resistance.

[Requirements (X-8)]
Requirement (X-8) stipulates that a molded product of the composition (X) having a thickness of 3 mm is used and the Vicat softening temperature measured according to ASTM D1525 is 100 ° C. or higher. The Vicat softening temperature can be specifically measured by the method described in the following Examples.
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 does not impair the heat resistance of the 4-methyl-1-pentene polymer and is excellent in heat resistance.

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. It is more preferably 205 to 250 ° C, particularly preferably 210 to 245 ° C.
Specifically, the Tm can be measured by the method described in the following Examples.

The comonomer content of the composition (X) is preferably 1.5 to 5.0 mol%, more preferably 1.7 to 4.5 mol%, and particularly preferably 1.9 to 4.0 mol%. ..
When the comonomer content is in the above range, the impact resistance, rigidity, heat resistance and transparency are well-balanced. If the comonomer content is below 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 in the composition (X) when the total amount of the constituent units constituting the polymers (A) and (B) in the composition (X) is 100 mol%. It refers to the total content of the structural units other than the 4-methyl-1-pentene-derived structural units constituting the coalesced bodies (A) and (B). Specifically, the polymer (A) in which the content of the structural unit other than the structural unit derived from 4-methyl-1-pentene is A1 mol% is a mass%, and the structural unit derived from 4-methyl-1-pentene is used. The content of the comonomer in the composition containing b mass% (however, a + b = 100) of the polymer (B) in which the content of the constituent units other than the above is B1 mol% is calculated by (A1 × a + B1 × b) / 100. can do.
Specifically, A1 and B1 can be measured by the method described in the following Examples.

<4-Methyl-1-pentene (co) polymer (A)>
The polymer (A) is not particularly limited as long as it satisfies the following requirement (Aa), and is a homopolymer of 4-methyl-1-pentene (that is, the content of a structural unit derived from 4-methyl-1-pentene). (Polymer in which is 100 mol%), or a copolymer of 4-methyl-1-pentene and another olefin or monomer. Further, the polymer (A) may be a graft-modified product in which these homopolymers or copolymers are used as modified products and graft-modified with a polar monomer or a silane coupling agent.
The polymer (A) used in the composition (X) may be one kind or two or more kinds.

[Requirements (A-a)]
The requirement (A-a) is that the content of the structural unit (U1) derived from 4-methyl-1-pentene is 96.0 to 100 mol% with respect to all the structural units contained in the polymer (A). , Ethylene and α-olefins with 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), with a content of building blocks (U2) derived from olefins selected from the group of 4.0 to 0 mol%. Prescribe that there is.
The content of the constituent unit (U1) is preferably 97 to 100 mol%, more preferably 98.0 to 99.9 mol%, and the constituent unit (U1) is excellent in terms of 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 the following Examples, and can be adjusted by the amount of 4-methyl-1-pentene and the olefin added during the polymerization reaction.

Specific examples of the olefin serving as the structural unit (U2) include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, and 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, 1-eicosene and the like. 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 preferable, and 1-hexene, 1-hexadecene and 1-octadecene are particularly preferable from the viewpoint of transparency and handleability at the time of molding.
One type of these olefins may be used, or two or more types may be used.

The polymer (A) may have a structural unit derived from 4-methyl-1-pentene and a monomer other than the olefin as long as the effect of the present invention is 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, based on 100 parts by mass of the total of the structural units (U1) and (U2). is there.

The ultimate 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 in the above range, it is preferable in terms of resin fluidity during molding of the composition (X).
[Η _A ] can be adjusted by appropriately selecting the hydrogen concentration, pressure, etc. 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. It is more preferably 228 to 245 ° C, and particularly preferably 230 to 245 ° C.
The Tm is determined by a differential scanning calorific value measurement (heating rate: 10 ° C./min). The Tm can be arbitrarily adjusted by appropriately selecting the comonomer species and the amount thereof.

<4-Methyl-1-pentene copolymer (B)>
The polymer (B) is a polymer other than the polymer (A), and is not particularly limited as long as the following requirements (BA) are satisfied, and 4-methyl-1-pentene is coexisted with other olefins and monomers. Examples include polymers. Further, the polymer (B) may be a graft-modified product in which this copolymer is used as a modified product and graft-modified with a polar monomer or a silane coupling agent.
The polymer (B) used in the composition (X) may be one kind or two or more kinds.

[Requirements (BA)]
The requirement (BA) is that the content of the structural unit (U3) derived from 4-methyl-1-pentene is 85.0 mol% or more and 96.0 with respect to all the structural units contained in the polymer (B). The content of the structural unit (U4) derived from an olefin selected from the group consisting of ethylene and α-olefin (excluding 4-methyl-1-pentene) having less than mol% and having 3 to 20 carbon atoms is 4.0. It is specified that it exceeds mol% and is 15.0 mol% or less.
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 being more excellent in impact resistance and the like. 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, specifically by the method described in the examples below, and 4-methyl-1-pentene added during the polymerization reaction 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 and 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 Examples thereof include -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, etc. Examples thereof include 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene, and 1-hexene, 1-hexadecene and 1-octadecene are particularly preferable from the viewpoint of transparency and handleability during molding.
As the olefin serving as the structural unit (U4), one type may be used, or two or more types may be used.

The polymer (B) may have a structural unit derived from 4-methyl-1-pentene and a monomer other than the olefin as long as the effect of the present invention is 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, based on 100 parts by mass of the total of the structural units (U3) and (U4).

The ultimate 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 in 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, pressure, and the like of the polymerization system.

The melting point (Tm) of the polymer (B) measured by DSC is preferably in the range of less than 220 ° C. or from the viewpoint that a composition having more excellent flexibility and heat resistance can be easily obtained. The peak indicating the melting point does not appear in the DSC measurement. When Tm is present, its temperature is more preferably less than 160 ° C, even more preferably less than 155 ° C.
The Tm is determined by a differential scanning calorific value measurement (heating rate: 10 ° C./min). The Tm can be arbitrarily adjusted by appropriately selecting the comonomer species and the amount thereof.

[Methods for producing polymers (A) and (B)]
The methods for producing the polymers (A) and (B) are not particularly limited, and for example, the methods described in International Publication No. 01/27124, International Publication No. 14/050817, and the like can be adopted.
Specifically, the polymers (A) and (B) can be obtained by polymerizing a predetermined monomer in the presence of a catalyst for olefin polymerization described later.

As the catalyst for olefin polymerization,
Cross-linked metallocene compound (A) and
At least one selected from (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with the metallocene compound (A) to form an ion pair, and (b-3) an organoaluminum compound. Compound (B) and
A catalyst containing is preferable.

-Cross-linked metallocene compound (A)
As the crosslinked 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 the formula [A1], M is a transition metal of Group 4 of the periodic table, for example, a titanium atom, a zirconium atom or a hafnium atom, and Q is independently a halogen atom, a hydrocarbon group, and a neutral having 10 or less carbon atoms. conjugated or nonconjugated diene, anionic ligand, or, a neutral ligand capable of coordination by lone pair, j is an integer of 1 to 4, R ^a and R ^B are each independently , M are mononuclear or multinucleated hydrocarbon residues capable of forming a sandwich structure, Y is a carbon atom or a silicon atom, ^RC and ^RD are independent hydrogen atoms and hydrocarbon groups, respectively. , A silicon-containing group, a halogen atom or a halogen-containing hydrocarbon group, and ^RC and ^RD may be bonded to each other to form a ring.

In the formula [A2], R ¹ is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R ^{2 to} R ¹⁰ are independently hydrogen atoms, hydrocarbon groups, silicon-containing groups, halogen atoms or It is a halogen-containing hydrocarbon group, of which two adjacent two may be bonded to each other to form a ring. M is a transition metal of Group 4 of the periodic table, and Q is independently a halogen atom, a hydrocarbon group, a neutral conjugated or unconjugated diene having 10 or less carbon atoms, an anionic ligand, or a lone electron pair. It is a neutral ligand that can be coordinated with, and j is an integer of 1 to 4.

Among the crosslinked metallocene compounds represented by the formula [A2], the crosslinked metallocene compound represented by the following formula [A3] is available from the viewpoints of polymerization characteristics, availability, and easy synthesis of a polymer satisfying the above requirements. Especially preferable.

In the formula [A3], R ^1b is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R ^{2b to} R ^12b are independently hydrogen atoms, hydrocarbon groups, silicon-containing groups, halogen atoms or It is a halogen-containing hydrocarbon group, and two adjacent groups may be bonded to each other to form a ring. M is a transition metal of Group 4 of the periodic table, n is an integer of 1-3, and Q is independently a halogen atom, a hydrocarbon group, a neutral conjugated or unconjugated diene having 10 or less carbon atoms. It is an anionic ligand or a neutral ligand that can be coordinated with a lone electron pair, and j is an integer of 1 to 4.

Examples of the hydrocarbon group include one or more hydrogen atoms contained in 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 hydrocarbon group usually has 1 to 20, preferably 1 to 15, and more preferably 1 to 10.

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

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

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

Examples of the cyclic unsaturated hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group and an anthrasenyl group; a cycloalkenyl group such as a cyclohexenyl group; 5-bicyclo [2.2. 1] Examples thereof include a polycyclic unsaturated alicyclic group such as a hepta-2-enyl (norbornenyl) group.

Examples of the group formed by substituting one or more hydrogen atoms of the 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. Examples thereof include a group formed 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-SiR ₃ (in the formula, each of the plurality of Rs has 1 carbon number independently. It is an alkyl group or a phenyl group of ~ 15).

Examples of the halogen-containing hydrocarbon group include a group formed by substituting one or more hydrogen atoms of the hydrocarbon group with a halogen atom, such as a trifluoromethyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of the substituents R ^{2 to} R ¹⁰ and R ^{2b to} R ^12b , two adjacent substituents (eg, R ^2b and R ^3b , R ^3b and R ^4b , R ^5b and R ^6b , R ^6b and R ^7b , R ^8b and R ^9b , R ^9b and R ^10b , R ^10b and R ^11b , R ^11b and R ^12b ) may be bonded to each other to form a ring, and there are two or more such rings in the molecule. It 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 thereof include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring and a cyclopentene ring, and preferably a cyclohexane ring, a benzene ring and a hydrogenated benzene ring. Further, 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. A group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group is particularly preferable, and a carbon having a free valence (carbon bonded to a cyclopentadienyl ring) is particularly preferably a tertiary carbon. ..

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, which are more preferable. Is a group in which the carbon having a free atomic value such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group and a 1-adamantyl group is a tertiary carbon, and particularly preferably a tert-butyl group and a 1-adamantyl group. It is the basis.

In the formula [A3], the fluorene ring moiety 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 a hydrogen atom or a hydrocarbon group, more preferably a hydrocarbon group, and even more preferably a hydrocarbon group having 1 to 20 carbon atoms. Further, R ^2b and R ^3b may be bonded to each other to form a ring, and R ^6b and R ^7b may be bonded to each other to form a ring. Examples of such 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] Fluolenyl groups are mentioned, and 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, and R ^9b is further 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. It is particularly preferable that R ^9b is an alkyl group having 2 or more carbon atoms. From a synthetic point of view, it is also preferable that R ^10b and R ^11b are hydrogen atoms.

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

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

As the hydrocarbon group in Q, an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms are preferable. As alkyl groups having 1 to 10 carbon atoms, 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 group having 3 to 10 carbon atoms include cyclohexylmethyl group, cyclohexyl group and 1-methyl-1-cyclohexyl group. More preferably, the hydrocarbon group has 5 or less carbon atoms.

The conjugated or non-conjugated diene having 10 or less of neutral atoms, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ^4-1,4- diphenyl-1,3-butadiene, s- cis - or s- trans eta ^{4-3-methyl-1,3-pentadiene,} s- cis - or s- trans eta ^{4-1,4-dibenzyl-1,} 3-butadiene, s- cis - or s- trans eta ^{4-2,4-hexadiene,} s- cis - or s- trans eta ^{4-1,3-pentadiene,} s- cis - or s- trans eta ⁴ -1,4-ditolyl-1,3-butadiene, s- cis - or s- trans eta ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

Examples of the anion ligand include an alkoxy group such as a methoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group; a carboxylate group such as an acetate group and a benzoate group; and a sulfonate group such as a mesylate group and a tosylate group. To.

Organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine; as neutral ligands that can be coordinated with isolated electron pairs; tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-dimethoxy Examples include ethers such as ethane.

A preferred embodiment of Q is a halogen atom or an alkyl group having 1 to 5 carbon atoms.

n is an integer of 1-3, preferably 1 or 2, and more preferably 1. It is preferable that n is these values from the viewpoint that the polymer can be efficiently synthesized.
j is an integer of 1 to 4, preferably 2.

Examples of the crosslinked metallocene compound represented by the 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.

-Organoaluminium oxy compound (b-1)
Examples of the organoaluminum oxy compound (b-1) include conventionally known aluminoxanes such as a compound represented by the following formula [B1] and a compound represented by the following formula [B2], and a structure represented by the following formula [B3]. A modified methylaluminoxane having the above, and a boron-containing organoaluminum oxy compound represented by the following formula [B4] are exemplified.
The compound (b-1) may be used alone or in combination of two or more.

In the 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, and more preferably 10 or more.
In the formulas [B1] and [B2], methylaluminoxane in which R is a methyl group is preferably used.

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

Also, from Tosoh Finechem Co., Ltd., modified methylaluminoxane prepared using trimethylaluminum and triisobutylaluminum (that is, R is an isobutyl group in the formula [B3]) is a product called MMAO or TMAO. It is commercially available under the name.

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

In the formula [B4], R ^c is a hydrocarbon group having 1 to 10 carbon atoms. Each of the plurality of R ^ds 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, a benzene-insoluble or sparingly soluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be used. In addition, organoaluminum oxy compounds described in JP-A-2-167305, and aluminoxane having two or more alkyl groups described in JP-A-2-24701 and JP-A-3-103407 are also available. Can be suitably used.

The above-mentioned "benzene-insoluble or sparingly soluble" organoaluminum oxy compound has a dissolved amount in benzene at 60 ° C., usually 10% by mass or less, preferably 5% by mass or less, particularly preferably. Refers to an organoaluminum oxy compound having an amount of 2% by mass or less.

-Compound (b-2) that reacts with the crosslinked metallocene compound (A) to form an ion pair
Examples of the compound (b-2) (hereinafter, also referred to as “ionic compound (b-2)”) that reacts with the crosslinked metallocene compound (A) to form an ion pair are disclosed in JP-A No. 1-501950. Kaihei 1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, JP-A-2004-51676, US Pat. No. Examples thereof include Lewis acid, an ionic compound, a borane compound and a carborane compound described in No. 5321106 and the like. Further, heteropoly compounds and isopoly compounds are also exemplified. Among these, the compound represented by the following formula [B5] is preferable.
The ionic compound (b-2) may be used alone or in combination of two or more.

In the formula [B5], as R e ⁺ is, H ^+, oxonium cation, carbenium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, is ferrocenium cation having a transition metal is exemplified. 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 carbocation cation include trisubstituted carbocation cations such as triphenyl carbocation cation, tris (methylphenyl) carbocation cation, and tris (dimethylphenyl) carbocation cation.

Examples of the ammonium cation include trialkylammonary cations such as trimethylammonium cation, triethylammonary cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation and triisobutylammonium cation; N, N. N, N-dialkylanilinium cations such as −dimethylanilinium cation, N, N-diethylanilinium cation, N, N, 2,4,6-pentamethylanilinium cation; diisopropylammonary cation, dicyclohexylammonium cation and the like Dialkylammonium cations are exemplified.

Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

In the above examples, as ^{Re +} , a carbocation cation and an ammonium cation are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

When Re ⁺ is a carbenium cation, triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-ditrifluoromethylphenyl) borate, tris ( Examples thereof include 4-methylphenyl) carbenium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of the case where Re ⁺ is an ammonium cation include a trialkylammonium salt, an N, N-dialkylanilinium salt, and a dialkylammonium salt.

Specific examples of the trialkylammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, and trimethylammonium tetrakis ( o-trill) 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, dioctadecylmethylammonium are exemplified.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and N, N-dimethylanilinium tetrakis. (3,5-Ditrifluoromethylphenyl) Borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5) -Ditrifluoromethylphenyl) borate, N, N, 2,4,6-pentamethylanilinium tetraphenylborate, N, N, 2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate are exemplified. To.

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

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

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

Examples of the organic aluminum compound [B6] include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, trin-butylaluminum, trihexylaluminum, and trioctylaluminum; triisopropylaluminum, triisobutylaluminum, and trisec-butylaluminum. Tri-branched alkylaluminum such as tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; triphenyl Triarylaluminum such as aluminum and tritrylaluminum; Dialkylaluminum hydride such as diisopropylaluminum hydride and diisobutylaluminum hydride; General formula (i-C ₄ H ₉ ) _{x A y} (C ₅ H ₁₀ ) _z (in the formula, x, Y and z are positive numbers, and z ≦ 2x.) Alkenyl aluminum such as isoprenyl aluminum; alkylaluminum alkoxides such as isobutylaluminum methoxyd and isobutylaluminum ethoxide; dimethylaluminum methoxyd, Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxydo and butylaluminum sesquibutoxide; formula R ^a _2.5 Al (OR ^b ) _0.5 (in the formula, ^Ra and R ^b). Is synonymous with ^Ra and R ^b in the formula [B6]) and has an average composition of partially alkoxylated alkylaluminum; diethylaluminum phenoxide, diethylaluminum (2,6-ditert-). Alkylaluminum aryloxides such as butyl-4-methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum sesquichloride, Alkyl aluminum sesquihalide such as ethyl aluminum sesquibromid; ethyl aluminum diclo Partially halogenated alkylaluminum such as alkylaluminum dihalide such as lid; dialkylaluminum hydride such as diethylaluminum hydride and dibutylaluminum hydride, alkylaluminum dihydride such as ethylaluminum dihydride and propylaluminum dihydride. Alkylaluminum hydrogenated; partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, ethylaluminum ethoxybromid; are exemplified.

M ² AlR ^a ₄ [B7]
In the formula [B7], M ² is Li, a Na or K, the plurality of R ^a each independently 1 to 15 carbon atoms, preferably 1-4 hydrocarbon group.

Examples of the complex alkylated product [B7] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Further, a compound similar to the complex alkylated product [B7] can also be used, and an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom is exemplified. Examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

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

-Carrier (C)
The carrier (C) may be used as a component of the catalyst for olefin polymerization. The carrier (C) is an inorganic compound or an organic compound, and is a solid in the form of granules or fine particles.
The carrier (C) may be used alone or in combination of two or more.

Examples of the inorganic compound include porous oxides, inorganic halides, clay minerals, clays (usually composed mainly of the clay minerals), and ion-exchangeable layered compounds (most clay minerals are ion-exchangeable). It is a layered compound.) Is exemplified. Examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ ; a composite or mixture containing these oxides. .. As a composite or mixture, natural or synthetic zeolite, 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, a porous oxide containing one or both components of SiO ₂ and Al ₂ O ₃ as a main component is preferable.

The porous oxide has different properties depending on the type and manufacturing method, but the particle size 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 100-700 m ² / g; the pore volume is preferably 0.3-3.0 cm ³ / g. Such a porous oxide is used by firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the inorganic halide include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill, a vibration mill or the like. Further, it is also possible to use a component obtained by dissolving the inorganic halide in a solvent such as alcohol and then precipitating it into fine particles with a precipitant.

As the clay, clay mineral, and ion-exchange layered compound, not only naturally produced ones but also artificial synthetic compounds can be used. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged.

Specifically, as clay and clay minerals, kaolin, bentonite, wood section clay, gailome clay, allophen, hisingel stone, pyrophyllite, ummo group such as synthetic mica, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, Examples include kaolinite, naclite, dicite, hectrite, teniolite, and haloysite; ion-exchangeable layered compounds include ions having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl ₂ type, and CdI ₂ type. Crystalline compounds are exemplified. Specifically, the ion-exchange layered _{compounds, α-Zr (HAsO 4)} 2 · H 2 O, α-Zr (HPO 4) 2, α-Zr (KPO 4) 2 · 3H 2 O, α- Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , Γ-Ti (NH ₄ PO ₄ ) ₂ , H ₂ O, and other crystalline acidic salts of polyvalent metals are exemplified.

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

Further, the ion-exchangeable layered compound may be a layered compound in which the layers are expanded by utilizing the ion-exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. For example, by intercalating the following metal hydroxide ions between the layers of the layered compound and then dehydrating by heating, oxide columns (pillars) can be formed between the layers. Introducing another substance between the layers of the layered compound in this way is called intercalation.

As guest compounds to be intercalated, cationic inorganic compounds such as TiCl ₄ , ZrCl ₄ ; and metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group, etc.); [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^{+ and} other metal hydroxide ions Is exemplified. These guest compounds may be used alone or in combination of two or more.

Further, when the guest compound is intercalated, metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , and Ge (OR) ₄ (R is a hydrocarbon group or the like) are hydrolyzed and polycondensed. It is also possible to coexist a polymer, a colloidal inorganic compound such as SiO _{2, and the} like.
Among the inorganic compounds, clay minerals and clays are preferable, and montmorillonite group, vermiculite, hectorite, teniolite and synthetic mica are particularly preferable.

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

-Organic compound component (D)
The organic compound component (D) may be used as a component of the catalyst for olefin polymerization. The organic compound component (D) is used for the purpose of improving the polymerization performance in the polymerization reaction of α-olefin and the physical properties of the olefin polymer, if necessary. 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.

-Construction of catalyst for olefin polymerization When polymerizing an olefin using the catalyst for olefin polymerization, the amount of each component that can constitute the catalyst for olefin polymerization is as follows, for example.

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

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

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

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

(5) When the organic compound component (D) is used as the 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)] to 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)] of the organic compound component (D) to the compound (b-2) is usually 0.01 to 10, preferably 0.01 to 10. In an amount such that it is 0.1 to 5; when the compound (B) is an organoaluminum compound (b-3), the molar ratio of the organic compound component (D) to the compound (b-3) [(D). / (B-3)] is usually used in an amount such that it is 0.01 to 2, preferably 0.005 to 1.

-Polymerization method The polymerization in the production of the polymers (A) and (B) can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a vapor phase polymerization method.
In the liquid phase polymerization method, an inert hydrocarbon medium may be used, and the inert hydrocarbon medium includes, for example, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Hydrogen; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane.
The inert hydrocarbon medium may be used alone or in combination of two or more. Further, a so-called bulk polymerization method in which the liquefied olefin itself that can be supplied for polymerization is used as a solvent can also be used.

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

The polymerization can produce a polymer having high stereoregularity, high melting point and high molecular weight while maintaining high catalytic activity even under high temperature conditions which are advantageous in the industrial production method. 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. (in other words, particularly preferably industrializable. It is the temperature.).

In particular, hydrogen can be said to be a preferable additive because it may have an effect of improving the polymerization activity of the catalyst and an effect of increasing or decreasing the molecular weight of the polymer. When hydrogen is added into the system, the amount thereof is appropriately 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 includes a method of performing a reaction that produces or consumes hydrogen in the system, a method of separating hydrogen using a membrane, and some hydrogen-containing methods. It can also be adjusted by releasing the gas out of the system.

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

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

Examples of the ethylenically unsaturated bond-containing monomer used for graft modification include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, and an unsaturated compound. Examples thereof include carboxylic acids or derivatives thereof, vinyl ester compounds, vinyl chlorides, and carbodiimide compounds. In particular, unsaturated carboxylic acids or derivatives thereof are preferred.

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

When a modified product is used as the polymer (A) or (B), the adhesiveness and compatibility with other resins are excellent, and the wettability of the obtained molded product surface may be improved. Further, by using the modified product, compatibility or adhesiveness with other materials (glass, metal, wood, etc.) other than the resin may be added.

Further, when a modified product in which the graft amount of the monomer (for example, unsaturated carboxylic acid and / or a derivative thereof) is in the above range is used, the composition (X) is composed of a polar group-containing resin (for example, polyester, polyvinyl alcohol, etc.). It exhibits high adhesive strength to ethylene / vinyl alcohol copolymers, polyamides, PMMAs, polycarbonates, etc.).

<Other ingredients>
The composition (X) may optionally contain an additive for a resin (hereinafter, also referred to as "additive (C)") as long as the effect of the present invention is not impaired, depending on its use. ..

<Additive (C)>
Examples of the additive (C) include nucleating agents, antiblocking agents, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, and surfactants. Agents, antistatic agents, weather stabilizers, heat stabilizers, antislip agents, foaming agents, crystallization aids, antifogging agents, antiaging agents, hydrochloric acid absorbers, impact modifiers, crosslinkers, co-crosslinkers, crosslinks Auxiliary agents, adhesives, softeners, processing aids, dispersants can be mentioned.
The additive (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 the object of the present invention is not impaired, 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 preferable.

As the nucleating agent, a known nucleating agent can be used in order 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, benzoate metal salt-based nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di-t). -Butylphenyl) sodium phosphate, pimeric acid and its salts, 2,6-naphthalene acid dicarboxylic acid dicyclohexylamide, ethylene bisstearate amide and the like can be mentioned.

The blending 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 appropriately added at the time of producing the polymer, after the polymerization, or during the molding process.

As the anti-blocking agent, a known anti-blocking agent can be used. Specifically, fine powder silica, fine powder aluminum oxide, fine powder clay, powdery or liquid silicon resin, tetrafluoroethylene resin, fine powder crosslinked resin, for example, crosslinked acrylic, methacrylic resin powder, amido-based lubricant, etc. Can be mentioned. Of these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferable.

Examples of the pigment include inorganic pigments (eg, titanium oxide, iron oxide, chromium oxide, cadmium sulfide) and organic pigments (eg, azolake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of the dye include azo type, anthraquinone type, triphenylmethane type and the like. The amount of these pigments and dyes added is not particularly limited, but is usually 5% by mass or less, preferably 0.1 to 3% by mass, in total with respect to the total mass of the composition (X).

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

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

Examples of the plasticizer include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methylacetyllithinolate, etc.), aliphatic dialbonic acid esters (adipic acid-propylene glycol-based polyester, etc.), and aliphatic compounds. Examples thereof include tricarboxylic acid esters (triethyl citrate, etc.), phosphoric acid triesters (triphenyl phosphate, etc.), epoxy fatty acid esters (epoxybutyl stearate, etc.), and petroleum resins.

Examples of the release agent include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4-30) (hardened paraffin oil, etc.), glycol esters of fatty acids, and fluidized fatty acids. Paraffin is mentioned.

As the antioxidant, a known antioxidant can be used. Specifically, phenol-based (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenol-based (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 acid, etc.), amine-based (N, N-diisopropyl-p-phenylenediamine, etc.), lactone-based antioxidants, and the like.

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

Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based ultraviolet absorbers.
Examples of the antibacterial agent include a quaternary ammonium salt, a pyridine compound, an organic acid, an organic acid ester, a halogenated phenol, and an organic iodine.

Examples of the surfactant include nonionic, anionic, cationic or amphoteric surfactants. Examples of the nonionic surfactant include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, and polypropylene glycol ethylene oxide adduct, polyethylene oxide, and glycerin. Examples thereof include polyhydric alcohol type nonionic surfactants such as fatty acid esters, pentaerythritol fatty acid esters, sorbit or sorbitan fatty acid esters, polyhydric alcohol alkyl ethers, and alkanolamine aliphatic amides. Examples of the anionic surfactant include sulfate esters such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates and paraffin sulfonates, and higher alcohol phosphate esters. Phosphate ester salt can be mentioned. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric surfactant include amino acid-type double-sided surfactants such as higher alkylaminopropionate, higher alkyldimethylbetaine, and betaine-type amphoteric surfactants such as hydroxyethyl betaine when higher alkylated.

Examples of the antistatic agent include the above-mentioned surfactant, fatty acid ester, and polymer type antistatic agent. Examples of the fatty acid ester include esters of stearic acid and oleic acid, and examples of the polymer antistatic agent include polyether ester amides.

Examples of the heat-resistant stabilizer 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; dibutylhydroxytoluene and tetrakis [methylene (3,5-di-t-). Butyl-4-hydroxy) hydrocinnamate] Phenolic stabilizers such as methane, octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; bis [2-methyl-4- (3-) N-alkylthiopropionyloxy) -5-t-butylphenyl] thioether-based stabilizers such as sulfides; dithiocarbamate-based stabilizers such as nickel dibutyldithiocarbamate; zinc salts of 2-mercaptobenzoylimidazole and 2-mercaptobenzoimidazole; Examples thereof include sulfur-based stabilizers such as dilaurylthiodipropionate and distearylthiodipropionate. These stabilizers may be used alone or in combination of two or more.

As the cross-linking agent, for example, an organic peroxide is used.
Examples of the organic peroxide include dicumyl organic peroxide, di-tert-butyl organic peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-di. -(Tert-butylperoxy) hexin-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl- 4,4-Bis (tert-butylperoxy) peroxide, 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-butylcumyl organic peroxide.

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

In the cross-linking treatment with organic peroxide, sulfur, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, tri Peroxy cross-linking aids such as methylolpropane-N, N'-m-phenylenedi maleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylpropantrimethacrylate, allyl Polyfunctional methacrylate monomers such as methacrylate and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

By using the above compound, a uniform and mild cross-linking reaction can be expected. Of these, divinylbenzene is particularly preferably used. Divinylbenzene is easy to handle, has good compatibility with polymers (A) and (B), has an action of solubilizing organic peroxide, and acts as a dispersant for organic peroxide. Therefore, a homogeneous cross-linking effect can be obtained, and a dynamic heat-treated product having a good balance between 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 with respect to 100 parts by mass of the total amount of the polymers (A) and (B).

Examples of the softening agent include mineral oil-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and vaseline, hydrocarbon-based softeners such as hydrocarbon and colital pitch, castor oil, and rapeseed oil. Fatroleum-based softeners such as soybean oil and coconut oil, waxes such as tall oil, dense wax, carnauba wax, and lanolin, fatty acids such as ricinolic acid, palmitic acid, stearic acid, barium stearate, and calcium stearate, or metal salts thereof. Synthetic polymer substances such as naphthenic acid or its metal soap, pine oil, rosin or its derivatives, terpene resin, petroleum resin, kumaron inden resin, atactic polypropylene, and ester-based plastics such as dioctylphthalate, dioctyl adipate, and dioctyl sebacate Agents, carbonate ester-based plasticizers such as diisododecyl carbonate, and other examples include microcrystalin wax, sub (factis), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, and hydrocarbon-based synthetic lubricating oil. Among these, petroleum-based softeners and hydrocarbon-based synthetic lubricating oils are preferable.

The amount of the softener is not particularly limited, but is preferably 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 when preparing the composition (X) and assists in the dispersion of carbon black and the like.

<Manufacturing method of composition (X)>
The method for producing the composition (X) is not particularly limited, but for example, the polymers (A) and (B) and, if necessary, other optional components are mixed at the above-mentioned addition ratios and then melt-kneaded. Can be obtained at.

The method of melt-kneading is not particularly limited, and it can be carried out by using a melt-kneading device such as a generally commercially available extruder.
For example, the cylinder temperature of the portion to be kneaded 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 the components such as the polymers (A) and (B) may occur.

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

As the molding method of the composition (X), various known molding methods can be applied, for example, injection molding, extrusion molding, injection stretching blow molding method, blow molding method, cast molding method, calendar molding method, press molding, etc. Various molding methods such as stamping molding, inflation molding, and roll molding can be mentioned. By these molding methods, it is possible to process a target molded product, for example, a film, a sheet, a hollow molded product, an injection molded product, a fiber, or the like. The molding conditions are the same as the molding conditions of the conventionally known 4-methyl-1-pentene polymer. There are no particular restrictions on the shape of the molded product. For example, it has a tube shape, a film shape, a sheet shape, a membrane shape, a tape shape, a plate shape, a rod shape, a fibrous shape, and a non-woven fabric shape.

The composition (X) and the molded product can be used without limitation in applications in which a conventional 4-methyl-1-pentene polymer has been used, but impact resistance, rigidity, heat resistance and transparency can be used. Is more suitable for applications that require.
Specific applications include, for example, containers, films, and packaging materials.

Examples of containers include tableware, food containers, tampering containers, kitchen utensils, retort containers, frozen storage containers, retort pouches, microwave heat-resistant containers, microwave steam sterilization containers, frozen food containers, chilled confectionery cups, cups, etc. Infant supplies (eg baby bottles), bottle containers, medical equipment, (eg 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, bleaching agents containers, shampoo containers, rinse 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 the film include, for example, packaging materials for foods (eg, meat, processed fish, vegetables, fruits, fermented foods, retort foods, confectionery, medicines, bulbs, seeds, mushrooms), wrap films, cell culture bags, etc. Examples include cell test films, heat-resistant vacuum-formed containers, prepared food containers, prepared food lids, baking cartons, and various release films.

Further, as the film, for example, a release film for a flexible printed substrate, a release film for an ACM substrate, a release film for a rigid substrate, a release film for a rigid flexible substrate, a release film for an advanced composite material, and a carbon fiber composite material. Release film for curing, release film for curing glass fiber composite material, release film for curing aramid fiber composite material, release film for curing nano composite material, release film for curing filler filler, release for semiconductor encapsulation Film, release film for polarizing plate, release film for diffusion sheet, release film for prism sheet, release film for reflection sheet, cushion film for release film, release film for fuel cell, release for various rubber sheets Release film such as film, release film for urethane curing, release film for epoxy curing, solar cell sealing sheet, solar cell back sheet, plastic film for solar cell, battery separator, separator for lithium ion battery, fuel Substrate / adhesive / separator of semiconductor process film such as electrolyte film for batteries, adhesive / adhesive separator, light guide plate, optical disk, dicing tape / back grind tape / dibonding film, double layer FCCL, film for film condenser, Adhesive film, stress relief film, pellicle film, polarizing plate film, polarizing plate protective film, liquid panel protective film, optical component protective film, lens protective film, electrical component / electrical appliance protective film, portable Protective film for telephones, protective film for personal computers, protective film for touch panels, protective film for window glass, film for baking finish, masking film, film for condensers, capacitor film, tab lead film, capacitor film for fuel cells, reflective film, diffusion film, Laminated body (including glass), radiation resistant film, γ-ray resistant film, protective film such as porous film, heat dissipation film / sheet, mold for manufacturing electronic component encapsulant, LED mold, laminated board for high frequency circuit, high frequency cable Coating material, optical waveguide substrate, glass fiber composite, carbon fiber composite, glass interlayer film, laminated glass film, window film for building materials, arcade dome, gymnasium window glass substitute, LCD substrate film, bulletproof material, bulletproof glass Film, heat shield sheet, heat shield film, release paper for synthetic leather, release paper for advanced composite material, release paper for curing carbon fiber composite material, glass fiber composite material hard Release paper for chemical conversion, release paper for curing aramid fiber composite material, release paper for curing nano composite material, release paper for curing filler filler, heat-resistant and water-resistant printing paper, packaging film, release film, breathable film , Reflective film, synthetic paper, display film, display conductive film, display barrier film and the like.

Examples of packaging materials include food packaging materials (eg, meat packaging materials, processed fish packaging materials, vegetable packaging materials, fruit packaging materials, fermented food packaging materials, confectionery packaging materials, oxygen absorber packaging materials, retort food packaging materials). ), Freshness-preserving film, medical packaging material, pharmaceutical packaging material, cell culture bag, cell test film, bulb packaging material, seed packaging material, vegetable / mushroom cultivation film, heat-resistant vacuum-molded container, side dish container, side dish lid material , Commercial wrap film, household wrap film, baking carton.

Other applications include, for example, rubber hose manufacturing mandrel, sheath, rubber hose manufacturing sheath, hose, tube, synthetic leather release paper, medical tube, industrial tube, cooling water pipe, hot water pipe, wire coating material, millimeter. Wave signal cable coating material, high frequency signal cable coating material, eco-wire coating material, in-vehicle cable coating material, signal cable coating material, high-pressure wire porcelain, wiring duct, cosmetic / perfume spray tube, medical tube, infusion tube, Pipes, wire harnesses, interior / exterior materials for automobiles / motorcycles / railway vehicles / aircraft / ships, etc., wear-resistant automobile interior / exterior materials, instrument panel skins, door trim skins, rear package trim skins, ceiling skins, rear pillar skins, seats Back garnish, console box, armrest, air bag case lid, shift knob, assist grip, side step mat, meter cover, battery cap, fuse, automatic flush sensor parts, ignition, coil bobbin, bushing, bumper, car heater fan, radiator grill, Wheel cap, EV power connector, in-vehicle display polarizing plate, louver, armrest, rail insulation plate, two-wheeled vehicle windproof, reclining cover, trunk seat, seat belt buckle, inner / outer molding, bumper molding, side molding, roof molding, Mole materials such as belt moldings, automobile sealing materials such as air spoilers, door seals, and body seals, glass run channels, mudguards, kicking plates, step mats, number plate housings, automobile 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 boots, glass guide, inner belt line seal, roof guide , Trunk lid seal, Molded quarter wind gasket, Corner molding, Glass encapsulation, Hood seal, Glass run channel, Secondary seal, Bumper parts, Body panel, Side shield, Door skin, Weather strip material, Hose, Steering wheel , Wire harness cover, seat adjuster cover, etc. Interior / exterior materials for moving vehicles, vibration damping tires, static tires, car race tires, radiocon tires and other special tires, packing, automobile dust covers, lamp seals, automobile boot materials, rack and pinion boots, timing belts, wire harnesses, glomet , Empreme, air filter packing, automotive connector, ignition coil, switch, lamp reflector, relay, electric control unit case, sensor housing, head lamp, meter plate, bearing retainer, thrust washer, lamp reflector, door handle, glazing, panorama Roofs, Solenoy valves, ECU cases, unit connection connectors, alternators, HEV terminal blocks, electromagnetic valves, coil encapsulation parts, skin materials for furniture, footwear, clothing, bags, building materials, etc., building sealants, waterproof sheets, building materials Sheets, pipe joints, dressing tables, bathroom ceilings, impellers, building material gaskets, window films for building materials, iron core protection members, ground improvement sheets, water blocking materials, joint materials, gaskets, doors, door frames, window frames, peripheral edges , Gaskets, opening frames, floor materials, ceiling materials, wallpaper, health products (eg non-slip mats / sheets, fall prevention films / mats / sheets), health equipment parts, shock absorbing pads, protectors / protective equipment (eg : Helmet, guard), sports equipment (eg sports grip, protector), sports armor, racket, mouth guard, ball, golf ball, carrying equipment (eg carrying shock absorbing glyph, shock absorbing sheet), vibration 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 tools, tools, exercise tools, vehicle handles, daily necessities, electric appliances, furniture , Etc.), camera body, camera parts, OA equipment parts, copying machine structural parts, printer structural parts, aircraft parts, in-flight food trays, facsimile structural parts, pump parts, electric tool parts, drying washing machine parts, heater pump injection Outlet / take-out port, IH rice cooker, rice cooker inner lid, range roller staying, vacuum cleaner fan guide, electronic jar pump / filter case, food waste disposer parts / treatment tank / heating / drying parts, milk meter, 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 supply parts, water cylinders, combs, pencil cases, pencil cases, pencil sharpeners, sports and leisure equipment, ski goggles, karate / kendo armor, surfing fins, musical instruments, fish tanks, sandals, snow scraping scoops, fishing rod cases, toys, Shoe sole, sole sole, midsole / inner sole of shoes, sole, sandals, chair skin, bag, land cell, jumper coat and other clothing, band, stick, ribbon, notebook cover, book cover, key holder, pencil case, Wallet, chopsticks, goggles, microwave cooking pan, business card holder, regular holder, sucker, toothbrush, floor material, gym mat, power tool material, agricultural machinery material, heat dissipation material, transparent substrate, soundproof material, sound absorbing material, cushioning material, Wire cables, shape memory materials, connectors, switches, plugs, home appliances parts (motor parts, housings, etc.), medical gaskets, speaker vibration plates, medical caps, chemical plugs, gaskets, baby food, dairy products, pharmaceuticals, sterile water Packing materials for high temperature treatment such as boiling treatment, high pressure steam sterilization, etc. after filling bottles, industrial sealing materials, industrial sewing tables, number plate housings, cap liners such as PET bottle cap liners, protective film adhesive layer , Adhesive materials such as hot melt adhesive materials, stationery, office supplies, OA printer legs, FAX legs, sewing machine legs, motor support mats, precision equipment / OA equipment support members such as audio anti-vibration materials, heat-resistant packing for OA, animal cages , Beakers, physics and chemistry experimental equipment such as female cylinders, medical film sheets, cell culture film sheets, syringes, optical media such as CD / DVD / Blu-ray, optical measurement cells, costume cases, clear cases, clear files, clear Sheet, desk mat, artificial cardiopulmonary, syringe syringe, three-way stopper, infusion set, surgeon's instrument, flow meter, dental instrument, contact lens sterilization instrument, inhalation mask, analytical cell, milking machine, fire alarm, fire extinguisher , Helmets, protective goggles, IC carriers, pickup lenses, burn-in sockets can be raised.

The composition (X) and the molded product can also be used as fibers.
Applications as fibers include, for example, monofilaments, multifilaments, cut fibers, hollow fibers, non-woven fabrics, stretchable non-woven fabrics, fibers, waterproof cloths, breathable textiles and cloths, paper diapers, sanitary goods, sanitary goods, filters, bag filters, etc. Examples include dust collection filters, air cleaners, hollow fiber filters, water purification filters, cloths, papers, gas separation membranes, artificial livers (cases, hollow fibers), and filter back-penetration membranes.

Further, the composition (X) and the molded product are a coating material, a film obtained by coating, a sheet, a mold release material, a water-shooting material, an insulating film, an adhesive, an adhesive material, a coated paper, a transparent sealant, a sealant, and a hot material. It is also suitably used for melt type adhesives, solvent type adhesives, film adhesives, cloth tapes, kraft tapes, elastic adhesives and the like.

Further, the composition (X) can also be processed into a fine powder by a pulverization treatment. The obtained fine powder can be used, for example, as an additive for an ink composition or a coating composition, as an additive for a metallurgical powder composition, as an additive for a ceramic sintering powder composition, or as an additive for a pressure-sensitive adhesive. It can be used as an additive for rubber, as a mold release agent for toner, as a mold release agent, and the like. Furthermore, the obtained fine powder can be used as a resin additive for shafts, gears, cams, electrical parts, camera parts, automobile parts, household parts, wax, grease, engine oil, fine ceramics, plating, etc. It can also be used as a resin additive for.

Although the present invention will be described in detail based on examples, 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. 2006/054613, the content of the structural unit derived from 4-methyl-1-pentene and 1-decene of the obtained copolymer is set to the content shown in Table 1 below. , 4-Methyl-1-pentene / 1-decene copolymer (A1) was obtained by changing the amount of the monomer charged.

[Production Example 2] 4-Methyl-1-pentene / 1-hexadecene / 1-octadecene copolymer (A2)
According to Synthesis Example 4 of WO2014 / 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 stir bar was placed in a Schlenk tube that had been sufficiently dried and replaced with nitrogen, 5.0 μmol of the metallocene compound (a) was placed, and a suspension of modified methylaluminoxane was 300 eq / cat. (N-hexane solvent, 1.50 mmol in terms of aluminum atom) was added at room temperature with stirring, 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.

4-Methyl-1-pentene 500 mL, cyclohexane 250 mL, linearene 168 (manufactured by Idemitsu Kosan Co., Ltd.) (1-hexadecene and 1-octadecene) in a SUS autoclave with an internal volume of 1,500 ml that has been sufficiently dried and replaced with nitrogen. 1.7 mL of the mixture) and 0.5 mmol of a hexane solution of triisobutylaluminum (Al concentration: 0.5 M) were charged, 124.3 mL of hydrogen was added, and then the polymerization temperature was 60 with stirring at 850 rpm. The temperature was raised to ° C.

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

The polymerization solution taken out from the cooled / depressurized autoclave was put into a 1: 1 solution of acetone and methanol to precipitate the polymer, which was recovered by filtration. Then, 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 copolymer (A3 to A6 and B1 to B6)
The charge amounts of 4-methyl-1-pentene and linearene 168 were changed so that the contents of the structural units derived from 1-hexadecene and 1-octadecene were the values shown in Table 1 or 2, and the charge of 4-methyl-1-pentene and linearene 168 was changed. 4-Methyl-1-pentene / 1-hexadecene / 1-octadecene copolymers (A3) to (A6) and (B1) to (B6) in the same manner as in Production Example 2 except that the charge amount was changed. Got

<Measurement of copolymer composition>
The content of the structural unit derived from each monomer in the copolymer obtained in the above production example was calculated from the ¹³ C-NMR spectrum by the following equipment and conditions.

An AVANCE III cryo-500 type nuclear magnetic resonance apparatus manufactured by Bruker Co., Ltd. was used as an apparatus, and an o-dichlorobenzene / benzene-d ₆ (4/1 v / v) mixed solvent was used as a solvent, and a sample concentration: 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 μsec (45 ° pulse), repetition time: 5.5 seconds, number of integrations: The peak of 128 ppm of benzene-d ₆ was measured as a reference value for chemical shift under the condition of 64 times. The content (mol%) of the structural unit derived from each monomer was calculated using the integrated value of the main chain methine signal. The results are shown in Table 1 or 2.
In these tables, the content of the structural unit derived from 4-methyl-1-pentene is referred to as 4-methyl-1-pentene content, which is derived from a monomer (comoner) other than 4-methyl-1-pentene. The total content of the constituent units is called the comonomer content.

<Measurement of extreme viscosity [η]>
The ultimate viscosity [η] was measured at 135 ° C. using a 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. After diluting with 5 ml of a decalin solvent added to this decalin solution, the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated twice more, and the value (dl / g) of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity (see the following formula).
The [η] of the copolymers obtained in Production Examples 1 to 6 was designated as [η _A ], and the [η] of the copolymers obtained in Production Examples 7 to 12 was designated as [η _B ]. The 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 combined with a twin-screw extruder (PCM43, manufactured by Ikegai Co., Ltd., screw diameter: 43 mm, temperature: 280 ° C., so as to have the composition composition shown in Table 3 below. A polymer composition was obtained by melt-kneading using (rotation speed: 200 rpm).

The obtained polymer composition was subjected to a thickness of 0.5 mm under the conditions of a cylinder temperature: 280 ° C. and a mold temperature: 60 ° C. using a 70-ton injection molding machine (M70B) manufactured by Meiki Seisakusho Co., Ltd. An injection test piece was prepared by injecting into a 2 mm, 3 mm or 1/4 inch square plate.
The following test was performed using this injection test piece.

<Melting point (Tm)>
The heat generation / endothermic curve was obtained by a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., and the temperature at the maximum melting peak position at the time of temperature rise was defined as the melting point (Tm). The measurement was performed as follows.
Approximately 5 mg of the sample was cut out from a 0.5 mm thick injection test piece, filled 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 10 The temperature is lowered to 20 ° C. at a cooling rate of ° C./min, held at 20 ° C. for 5 minutes, then raised again 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 temperature rise was defined as the melting point (Tm).

<Tensile test>
Using an injection test piece with a thickness of 2 mm, an ASTM-4 dumbbell type test piece was prepared in accordance with ASTM D638, and a tensile speed: 50 mm / min, measurement temperature was measured with a universal tensile tester 3380 manufactured by Instron. A tensile test was carried out under the condition of 23 ° C., and the tensile elastic modulus (YM) was measured.

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

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

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

<Vicat softening temperature test>
Using a 3 mm thick injection test piece, in accordance with ASTM D1525, using an HDT measuring device manufactured by Yasuda Seiki Seisakusho Co., Ltd., in silicone oil, temperature rise rate: 50 ° C. per hour, test load: 10 N A Vicat softening temperature test was carried out under the conditions, and the Vicat softening temperature was measured.

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

[Morphology observation]
The core portion (inside) of the injection test piece having a thickness of 2 mm was thinly scraped and observed with a transmission electron microscope manufactured by JEOL Ltd. 100 island fauna with a sea-island structure were observed, and the average of the longest diameter and the shortest diameter of each of the top 10 island fauna with a large area was used as the dispersion diameter. Specifically, it was calculated by the following formula.
Dispersion diameter (μm) = (total of 10 longest diameters (μm) + total of 10 shortest diameters (μm)) / 20

Claims (4)

4-Methyl-1-pentene (co) polymer (A) 70.0 to 85.0% by mass satisfying the following requirement (Aa),
4-Methyl-1-pentene copolymer (B) 30.0 to 15.0% by mass (provided that the (co) polymer (A) and the copolymer (B) satisfy the following requirements (BA). The total is 100% by mass),
A polymer composition (X) that satisfies the following requirements (X-1).
Requirement (A-a): The content of the structural unit derived from 4-methyl-1-pentene is 96.0 to 100 mol%, ethylene and α-olefin having 3 to 20 carbon atoms (4-methyl-1). The content of the structural unit derived from olefin selected from the group consisting of −pentene) is 4.0 to 0 mol% Requirement (BA): Constituent unit derived from 4-methyl-1-pentene The content is 85.0 mol% or more and less than 96.0 mol%, and the content of the structural unit derived from ethylene and α-olefin (excluding 4-methyl-1-pentene) having 3 to 20 carbon atoms is 4. Requirement (X-1) of more than 0.0 mol% and 15.0 mol% or less: Extreme viscosity of each of the (co) polymer (A) and the copolymer (B) measured in decalin at 135 ° C. [Η _A ] and [η _B ] satisfy the following equation 0.7 ≦ 1 / [η _A ] × ([η _A ] / [η _B ]) ^0.84 ≦ 5.3 The polymer composition (X) according to claim 1, which satisfies the following requirement (X-2).
Requirement (X-2): When observing 100 island fauna with a sea-island structure and adding the longest diameter and the shortest diameter of each of the top 10 island fauna with a large area and averaging them, the value is used as the dispersion diameter. The dispersion diameter is 0.3 to 3.0 μm. The polymer composition (X) according to claim 1 or 2, which satisfies at least one of the following requirements (X-3) to (X-6).
Requirement (X-3): The high-speed surface impact strength at 23 ° C. measured according to JIS K 7211 using a molded product of the composition (X) having a thickness of 2 mm is 4 to 20 J. Requirement (X-4): Requirement (X-5): Molding of composition (X) with a thickness of 2 mm using a molded product of composition (X) with a thickness of 3 mm and not being destroyed when an Izod impact test at 23 ° C. is performed in accordance with ASTM D256. Total light transmittance measured according to JIS K 7361 using a body is 90 to 98.0% Requirement (X-6): Using a molded product of a composition (X) having a thickness of 2 mm, in ASTM D638. The tensile modulus measured in accordance with this is 1000 to 2000 MPa. A molded product containing the polymer composition (X) according to any one of claims 1 to 3.