JP7273543B2 - Fibers and fiber structures - Google Patents

Description

TECHNICAL FIELD The present invention relates to fibers and fiber structures, and more particularly to fibers containing a 4-methyl-1-pentene copolymer, which are hard to break and have little fuzz, and fiber structures containing the same.

4-Methyl-1-pentene-based polymers containing 4-methyl-1-pentene as a main constituent monomer are widely used in various applications because of their excellent releasability and solvent resistance. For example, films are used for FPC release films, release films for composite material molding, etc., taking advantage of their features such as good releasability. Taking advantage of its features, it is used for wrap films, laboratory equipment, sheaths for manufacturing rubber hoses, mandrels, and raw materials for fibers.

Fibers made of a resin composition containing a 4-methyl-1-pentene polymer are suitable for use under high-temperature conditions, taking advantage of the heat resistance of the 4-methyl-1-pentene polymer. can be used. Furthermore, it is conceivable that the 4-methyl-1-pentene-based polymer can be used in applications that take advantage of various excellent physical properties such as acid resistance, alkali resistance, stain resistance, and lightness.

Patent Document 1 describes a polymethylpentene fiber having a single filament fineness of 3 dtex or less, U% (Normal) of less than 3, a total fineness of 500 dtex or less, and a strength of 2.0 cN/dtex or more. A process for producing polymethylpentene fibers is described in which the yarn is drawn 1.1-3.0 times at a drawing temperature of 150-220°C.

Patent Document 2 discloses a 4-methyl-1-pentene copolymer composition containing a 4-methyl-1-pentene (co)polymer (A) and a 4-methyl-1-pentene copolymer (B). (X) is described, and fibers are described as uses.
Patent Document 3 describes a fiber made of a resin composition containing a 4-methyl-1-pentene polymer.

JP 2017-014662 A JP 2018-162408 A JP 2015-183332 A

However, since the conventional polymethylpentene fiber has a small elongation, it breaks when it is processed into woven fabrics or knitted fabrics that are subjected to tension, which causes fluffing. Especially in apparel applications, fluffing causes poor appearance, so improvement of elongation and strength is an issue.
SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber that is less likely to break and has less fluff.

By alloying polymethylpentene with flexible polymethylpentene, which has a large amount of copolymer components, we succeeded in obtaining a fiber with improved elongation while maintaining the same level of strength as conventional polymethylpentene fiber. The present invention has been completed.

The present invention relates to the following [1] to [5].
[1] A fiber containing a 4-methyl-1-pentene copolymer and satisfying the following requirements (X-1) to (X-3).
(X-1) Elongation is 50 to 300%.
(X-2) Breaking strength is 2.0 to 7.0 cN/dtex.
(X-3) Single filament fineness is 0.5 to 1200 dtex.
[2] 5.0 to 95.0 parts by mass of a 4-methyl-1-pentene (co)polymer (A) satisfying the following requirements (Aa) and (Ab);
5.0 to 95.0 parts by mass of 4-methyl-1-pentene copolymer (B) satisfying the following requirements (Ba) and (Bb) (provided that (co)polymer (A) and The total with the polymer (B) is 100 parts by mass)
A 4-methyl-1-pentene copolymer composition (X) containing
Fibers that satisfy the following requirements (X-1) to (X-3).
(Aa) the content (U1) of structural units derived from 4-methyl-1-pentene is 96.0 mol% or more and 100 mol% or less;
The content (U2) of structural units derived from at least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 mol% or more4 0 mol % or less (provided that the total of (U1) and (U2) is 100 mol %).
(Ab) Melting point (Tm) measured by DSC is 200 to 240°C.
(Ba) the content (U3) of structural units derived from 4-methyl-1-pentene is 73.0 mol% or more and less than 96.0 mol%;
The content (U4) of structural units derived from at least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 4.0 mol% 27.0 mol % or less (provided that the total of (U3) and (U4) is 100 mol %).
(Bb) Melting point (Tm) measured by DSC is less than 230° C., or no peak indicating melting point appears in DSC measurement.
(X-1) Elongation is 50 to 300%.
(X-2) Breaking strength is 2.0 to 7.0 cN/dtex.
(X-3) Single filament fineness is 0.5 to 1200 dtex.
[3] Ethylene contained in the 4-methyl-1-pentene (co)polymer (A) and the 4-methyl-1-pentene copolymer (B) and an α-olefin having 3 to 20 carbon atoms ( 4-methyl-1-pentene) is at least one α-olefin structural unit selected from α-olefins having 10 to 20 carbon atoms, [2 ] The fiber according to .
[4] for all structural units contained in the polymer in the copolymer composition (X),
At least one selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) contained in the 4-methyl-1-pentene (co)polymer (A) a structural unit derived from an olefin of
At least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) contained in the 4-methyl-1-pentene copolymer (B) The fiber according to [2] or [3], wherein the total content ratio of structural units derived from is 0.5 to 20 mol%.
[5] A fiber structure at least partially including the fiber according to any one of [1] to [4].

Since the fibers of the present invention have a large elongation, they are less likely to break and have less fluff. The fiber of the present invention can be applied to various fiber structures by taking advantage of such characteristics.

The fiber of the present invention contains a 4-methyl-1-pentene copolymer and satisfies the following requirements (X-1) to (X-3).
The 4-methyl-1-pentene copolymer is preferably a structural unit derived from 4-methyl-1-pentene, ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1-pentene (excluding) contains a structural unit derived from at least one olefin selected from the group consisting of Specific examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl- 1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1- octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Among the ethylene and α-olefins having 3 to 20 carbon atoms, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene are preferred. These olefins may be used singly or in combination of two or more.

Requirement (X-1)
The fibers have an elongation of 50-300%. The elongation is preferably 70-280%, more preferably 100-260%. When the elongation of the fiber is within the above range, it is preferable because the fiber has little fluffing and good durability.
Elongation is a value calculated by the method described in Examples.

Requirement (X-2)
The fibers have a breaking strength of 2.0-7.0 cN/dtex. The breaking strength is preferably 2.0-5.0 cN/dtex, more preferably 2.0-4.0 cN/dtex. When the breaking strength of the fiber is within the above range, the fiber is less likely to break and is excellent in durability, which is preferable.
Breaking strength is a value calculated by the method described in Examples.

Requirement (X-3)
The fiber has a single filament fineness of 0.5 to 1200 dtex. The single yarn fineness is preferably 1.5 to 500 dtex, more preferably 4.0 to 500 dtex, still more preferably 400 to 500 dtex.

The single filament fineness is a value obtained by dividing the total fineness by the number of filaments of the fiber, and the total fineness is a value representing the thickness of the fiber using the mass of the fiber in a certain length. The single filament fineness and the total fineness are values calculated by the method described in Examples.

As a preferred embodiment of the fiber of the present invention, a 4-methyl-1-pentene (co)polymer (A) satisfying the following requirements (Aa) and (Ab), and the following requirements (Ba) and 4 containing 4-methyl-1-pentene copolymer (B) that satisfies (Bb) (where the total of (co)polymer (A) and copolymer (B) is 100 parts by mass) -methyl-1-pentene copolymer composition (X) and satisfying the above requirements (X-1) to (X-3).

[4-methyl-1-pentene (co)polymer (A)]
The 4-methyl-1-pentene (co)polymer (A) satisfies requirements (Aa) and (Ab).
(Aa) The content (U1) of structural units derived from 4-methyl-1-pentene is 96.0 mol% or more and 100 mol% or less, and ethylene and an α-olefin having 3 to 20 carbon atoms ( The content (U2) of structural units derived from at least one olefin selected from the group consisting of (excluding 4-methyl-1-pentene) is 0 mol% or more and 4.0 mol% or less (with the proviso that (U1) and (U2) as 100 mol%).

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

The content (U1) of structural units derived from 4-methyl-1-pentene with respect to all structural units contained in the 4-methyl-1-pentene (co)polymer (A) is preferably 97 to 100 mol%, more Preferably 98.5 to 100 mol%, the content of structural units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) ( U2) is preferably 0 to 3 mol %, more preferably 0 to 1.5 mol %.

When the 4-methyl-1-pentene (co)polymer (A) is a copolymer, specifically as ethylene and an α-olefin having 3 to 20 carbon atoms to be copolymerized with 4-methyl-1-pentene is ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1- Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1- Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Of these, preferred is at least one α-olefin selected from 10 to 20 α-olefins, specifically 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- octadecene and the like. These α-olefins may be used singly or in combination of two or more.

Structural units derived from 4-methyl-1-pentene in the 4-methyl-1-pentene (co)polymer (A), and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1 -pentene), 4-methyl-1-pentene added during the polymerization reaction, and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1-pentene ) can be adjusted by the amount of

The 4-methyl-1-pentene (co)polymer (A) is derived from a monomer other than ethylene and an α-olefin having 3 to 20 carbon atoms, as long as the requirements (Aa) and (Ab) are satisfied. You may have a structural unit. The upper limit of the content of structural units derived from other monomers is, for example, 10% by mass or less, preferably 5% by mass or less, with respect to 100% by mass in total of (U1) and (U2).
(Ab) Melting point (Tm) measured by DSC is 200 to 240°C.

Melting points (Tm) are determined by differential scanning calorimetry (heating rate: 10° C./min).
The melting point (Tm) of the 4-methyl-1-pentene (co)polymer (A) is preferably 225-240°C, more preferably 230-240°C. The melting point (Tm) can be arbitrarily adjusted by appropriately selecting the comonomer species and its amount. When the melting point (Tm) is within the above range, the obtained copolymer composition has excellent heat resistance.

The 4-methyl-1-pentene (co)polymer (A) preferably has a melt flow rate (MFR) of 5 to 400 g/10 minutes measured at 260°C under a load of 5 kg according to ASTM D1238. , 5 to 180 g/10 min.
The 4-methyl-1-pentene (co)polymer (A) may be a graft-modified (co)polymer obtained by graft-modifying the (co)polymer with a polar monomer, as long as it satisfies the above requirements. good.

[Method for producing 4-methyl-1-pentene (co)polymer (A)]
As the method for producing the 4-methyl-1-pentene (co)polymer (A), for example, the methods described in International Publication No. 01/27124, International Publication No. 14/050817, etc. can be employed. Conventionally known polymerization catalysts can be used in the method for producing the 4-methyl-1-pentene (co)polymer (A).

In addition, as the method for producing the 4-methyl-1-pentene (co)polymer (A), a production method similar to the method for producing the 4-methyl-1-pentene copolymer (B) described later can be adopted. can.

When the 4-methyl-1-pentene (co)polymer (A) is a graft-modified (co)polymer, the 4-methyl-1-pentene (co)polymer is added with an ethylenically unsaturated bond-containing monomer, A 4-methyl-1-pentene (co)polymer (A) can be produced by graft modification with an organic peroxide.

Polar monomers used for graft modification include, for example, hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or derivatives thereof. , vinyl ester compounds, vinyl chloride, and carbodiimide compounds. Unsaturated carboxylic acids or derivatives thereof are particularly preferred.

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

When a modified product is used as the 4-methyl-1-pentene (co)polymer (A), the adhesiveness and compatibility with other resins are excellent, and the surface wettability of the obtained molded article is improved. There is Further, by using a modified product, it may be possible to add compatibility or adhesiveness with other materials (glass, metal, wood, etc.) other than resins.

In addition, since the graft amount of the polar monomer (for example, unsaturated carboxylic acid and/or derivative thereof) is within the above range, the 4-methyl-1-pentene copolymer composition (X) is a polar group-containing resin ( For example, polyester, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyamide, PMMA, polycarbonate, etc.) exhibit high adhesive strength.

[4-methyl-1-pentene copolymer (B)]
4-Methyl-1-pentene copolymer (B) satisfies requirements (Ba) and (Bb).
(B-a) The content (U3) of structural units derived from 4-methyl-1-pentene is 73.0 mol% or more and less than 96.0 mol%, and ethylene and α- having 3 to 20 carbon atoms The content (U4) of structural units derived from at least one olefin selected from the group consisting of olefins (excluding 4-methyl-1-pentene) is greater than 4.0 mol% and not more than 27.0 mol% ( However, the total of (U3) and (U4) is 100 mol%).

The content (U3) of structural units derived from 4-methyl-1-pentene with respect to all structural units contained in the 4-methyl-1-pentene copolymer (B) is preferably 80 to 95 mol%, more preferably 85 to 95 mol% of the structural unit content (U4) derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), It is preferably 5 to 20 mol %, more preferably 5 to 15 mol %.

In the present invention, “ethylene” and “α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene)” are also referred to as “comonomers”. A structural unit derived from a comonomer may be a structural unit derived from one comonomer, or may be a structural unit derived from two or more comonomers.

It is preferable that (U3) and (U4) are within the above ranges, since the resulting composition exhibits high impact resistance.
Comonomer composition can be measured by IR or ¹³ C-NMR.

The content of each structural unit in the 4-methyl-1-pentene copolymer (B) is, for example, each olefin added during the polymerization reaction (e.g., 4-methyl-1-pentene, ethylene, carbon number 3 to 20 α-olefins other than 4-methyl-1-pentene).

Examples of α-olefins other than ethylene and 4-methyl-1-pentene having 3 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1- Hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

Of these, preferred is at least one α-olefin selected from 10 to 20 α-olefins, specifically 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- octadecene and the like.

A comonomer may be used individually by 1 type, and may use 2 or more types together.
4-methyl-1-pentene copolymer (B) is derived from other monomers other than ethylene and α-olefins having 3 to 20 carbon atoms, as long as requirements (Ba) and (Bb) are satisfied. It may have a structural unit that The upper limit of the content of structural units derived from other monomers is, for example, 10% by mass or less, preferably 5% by mass or less with respect to 100% by mass in total of (U3) and (U4).

(Bb) Melting point (Tm) measured by DSC is less than 230° C., or no peak indicating melting point appears in DSC measurement.
Melting points (Tm) are determined by differential scanning calorimetry (heating rate: 10° C./min).
The 4-methyl-1-pentene copolymer (B) preferably has a melting point (Tm) of less than 225°C, or does not show a peak indicating the melting point in DSC measurement, and has a melting point (Tm) of less than 223°C. or no peak indicating the melting point appears in the DSC measurement.

The melting point (Tm) can be arbitrarily adjusted by appropriately selecting the comonomer species and its amount. When the melting point (Tm) is within the above range, the obtained copolymer composition is excellent in flexibility and impact resistance.

The 4-methyl-1-pentene copolymer (B) preferably has a melt flow rate (MFR) of 4 to 400 g/10 minutes measured under a load of 5 kg at 260° C. in accordance with ASTM D1238. More preferably ~180 g/10 min.

[Method for producing 4-methyl-1-pentene copolymer (B)]
4-methyl-1-pentene copolymer (B) is prepared by reacting 4-methyl-1-pentene, ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl- 1-pentene) can be obtained by copolymerizing with at least one olefin selected from 1-pentene.

[1] Olefin polymerization catalyst As the olefin polymerization catalyst,
(A) a bridged metallocene compound;
(B) (b-1) an organoaluminumoxy compound,
(b-2) a compound that reacts with the metallocene compound (A) to form an ion pair, and
(b-3) A catalyst containing at least one compound selected from organoaluminum compounds is preferred.

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

式［Ａ１］中、Ｍは周期表第４族遷移金属、例えばチタン原子、ジルコニウム原子またはハフニウム原子であり、Ｑはハロゲン原子、炭化水素基、炭素数１０以下の中性の共役もしくは非共役ジエン、アニオン配位子および孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれ、ｊは１～４の整数であり、Ｒ^AおよびＲ^Bは、互いに同一かまたは異なっていてもよく、Ｍと共にサンドイッチ構造を形成することができる単核または多核炭化水素残基であり、Ｙは炭素原子またはケイ素原子であり、Ｒ^CおよびＲ^Dは、互いに同一かまたは異なっていてもよく、水素原子、炭化水素基、ケイ素含有基、ハロゲン原子およびハロゲン含有炭化水素基から選ばれ、互いに結合して環を形成していてもよい。

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

式［Ａ２］中、Ｒ¹は炭化水素基、ケイ素含有基またはハロゲン含有炭化水素基であり、Ｒ²～Ｒ¹⁰は水素原子、炭化水素基、ケイ素含有基、ハロゲン原子およびハロゲン含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、それぞれの置換基は互いに結合して環を形成してもよい。Ｍは周期表第４族遷移金属であり、Ｑはハロゲン原子、炭化水素基、炭素数１０以下の中性の共役もしくは非共役ジエン、アニオン配位子および孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれ、ｊは１～４の整数である。

In formula [A2], R ¹ is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R ² to R ¹⁰ are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group. and may be the same or different, and the respective substituents may be combined with each other to form a ring. M is a transition metal of Group 4 of the periodic table, Q is a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand and a neutral capable of being coordinated with a lone electron pair are selected from the same or different combinations of ligands, and j is an integer from 1 to 4;

Among the crosslinked metallocene compounds represented by the general formula [A2], the crosslinked metallocene compounds represented by the general formula [A3] are particularly preferable from the viewpoint of obtaining a polymer that satisfies the above requirements, such as polymerization properties and availability.

式［Ａ３］中、Ｒ^1bは炭化水素基、ケイ素含有基またはハロゲン含有炭化水素基であり、Ｒ^2b～Ｒ^12bは水素原子、炭化水素基、ケイ素含有基、ハロゲン原子およびハロゲン含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、それぞれの置換基は互いに結合して環を形成してもよい。Ｍは周期表第４族遷移金属であり、ｎは１～３の整数であり、Ｑはハロゲン原子、炭化水素基、炭素数１０以下の中性の共役もしくは非共役ジエン、アニオン配位子および孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれ、ｊは１～４の整数である。

In formula [A3], R ^1b is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, R ^2b to R ^12b are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group and may be the same or different, and the respective substituents may be combined with each other to form a ring. M is a Group 4 transition metal of the periodic table, n is an integer of 1 to 3, Q is a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anion ligand and It is selected in the same or different combinations from neutral ligands capable of coordinating with a lone pair of electrons, and j is an integer of 1-4.

<R ¹ to R ¹⁰ , R ^1b to R ^12b >
Examples of hydrocarbon groups for R ¹ to R ¹⁰ and R ^1b to R ^12b include linear hydrocarbon groups, branched hydrocarbon groups, saturated cyclic hydrocarbon groups, unsaturated cyclic hydrocarbon groups, and saturated hydrocarbon groups. A group obtained by substituting one or more hydrogen atoms of with a cyclic unsaturated hydrocarbon group. The number of carbon atoms in the hydrocarbon group is usually 1-20, preferably 1-15, more preferably 1-10.

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

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

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

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

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

Examples of the silicon-containing group for R ¹ to R ¹⁰ and R ^1b to R ^12b include the formula -SiR ₃ (wherein , and each of a plurality of R is independently an alkyl group having 1 to 15 carbon atoms or a phenyl group.).

Halogen-containing hydrocarbon groups for R ¹ to R ¹⁰ and R ^1b to R ^12b are obtained by substituting one or more hydrogen atoms of the above hydrocarbon groups with halogen atoms, such as a trifluoromethyl group. groups.

Halogen atoms in R ² to R ¹⁰ and R ^2b to R ^12b include, for example, fluorine, chlorine, bromine and iodine atoms.
Of the substituents R ² to R ¹⁰ and R ^2b to R ^12b , two substituents (e.g., R ^2b and R ^3b , R ^3b and R ^4b , R ^5b and R ^6b , R ^6b and R ^7b , R ^8b and R ^9b ; R ^9b and R ^10b ; R ^{10b and} R ^{11b ;} may

In the present specification, examples of the ring (spiro ring, additional ring) formed by combining two substituents include an alicyclic ring and an aromatic ring. Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring and a cyclopentene ring, preferably a cyclohexane ring, a benzene ring and a hydrogenated benzene ring. Moreover, such a ring structure may further have a substituent such as an alkyl group on the ring.

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

Specific examples of R ^1b include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group and a 1-adamantyl group, which are more preferred. is a tert-butyl group, tert-pentyl group, 1-methylcyclohexyl group, 1-adamantyl group, and the like. It is an adamantyl group.

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

R ^2b , R ^3b , R ^6b and R ^7b are preferably hydrogen atoms or hydrocarbon groups, more preferably hydrocarbon groups, still more preferably hydrocarbon groups having 1 to 20 carbon atoms. In addition, R ^2b and R ^3b may combine with each other to form a ring, and R ^6b and R ^7b may combine with each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2 ,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group, 1,1,3,3,6,6,8,8-octamethyl-2,3, 6,7,8,10-hexahydro-1H-dicyclopenta[b,h]fluorenyl group, 1',1',3',6',8',8'-hexamethyl-1'H,8'H-dicyclopenta [b,h]fluorenyl group, particularly preferably 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro- 1H-dibenzo[b,h]fluorenyl group.

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

Alternatively, when n=1, it is more preferable that R ^9b and R ^10b combine with each other to form a ring, and it is particularly preferable that the ring is 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.

<Regarding M, Q, n and j>
M is a Group 4 transition metal, for example Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Zr.
Q represents a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair.
Halogen atoms for Q include, for example, fluorine, chlorine, bromine, and iodine.

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

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

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

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

A preferred embodiment of Q is a halogen atom or an alkyl group having 1 to 5 carbon atoms.
n is an integer of 1 to 3, preferably 1 or 2, more preferably 1; It is preferable from the viewpoint of efficiently obtaining the produced polymer that n is the above value.

j is an integer of 1 to 4, preferably 2;
Preferred embodiments of the structure of the bridged metallocene compound represented by the general formula [A2] or [A3], ie, R ¹ to R ¹⁰ , R ^1b to R ^12b , M, n, Q and j have been described above. In the present invention, any combination of each preferred aspect is also a preferred aspect. Such a bridged metallocene compound can be suitably used to obtain the polymer of the present invention having the above physical properties.

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

<Compound (B)>
<<organoaluminum oxy compound (b-1)>>
Examples of the organoaluminumoxy compound (b-1) include conventionally known aluminoxanes such as the compound represented by the general formula [B1] and the compound represented by the general formula [B2], and the structure represented by the general formula [B3]. and a boron-containing organoaluminumoxy compound represented by the general formula [B4].

式［Ｂ１］および［Ｂ２］において、Ｒは炭素数１～１０の炭化水素基、好ましくはメチル基であり、ｎは２以上、好ましくは３以上、より好ましくは１０以上の整数である。式［Ｂ１］および［Ｂ２］において、Ｒがメチル基であるメチルアルミノキサンが好適に使用される。

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

式［Ｂ３］において、Ｍｅはメチル基であり、Ｒは炭素数２～１０の炭化水素基であり、ｍおよびｎはそれぞれ独立に２以上の整数である。複数あるＲは相互に同一でも異なっていてもよい。修飾メチルアルミノキサン［Ｂ３］は、トリメチルアルミニウムとトリメチルアルミニウム以外のアルキルアルミニウムとを用いて調製することができる。このような修飾メチルアルミノキサン［Ｂ３］は、一般にＭＭＡＯ（ｍｏｄｉｆｉｅｄ ｍｅｔｈｙｌ ａｌｕｍｉｎｏｘａｎｅ）と呼ばれている。ＭＭＡＯは、具体的には米国特許第４９６０８７８号および米国特許第５０４１５８４号で挙げられる方法で調製することが出来る。

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

Modified methylaluminoxane prepared using trimethylaluminum and triisobutylaluminum (that is, R is an isobutyl group in general formula [B3]) is also available from Tosoh Finechem Co., Ltd. under the trade names of MMAO and TMAO. is produced commercially in

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

式［Ｂ４］において、Ｒ^cは炭素数１～１０の炭化水素基である。複数あるＲ^dはそれぞれ独立に水素原子、ハロゲン原子または炭素数１～１０の炭化水素基である。上記オレフィン重合用触媒を用いた製法では、後述するような高温においても重合体を製造することができる。したがって、特開平２－７８６８７号公報に例示されているようなベンゼン不溶性または難溶性の有機アルミニウムオキシ化合物をも使用できることができる。また、特開平２－１６７３０５号公報に記載されている有機アルミニウムオキシ化合物、特開平２－２４７０１号公報、特開平３－１０３４０７号公報に記載されている２種以上のアルキル基を有するアルミノキサンなども好適に使用できる。

In formula [B4], R ^c is a hydrocarbon group having 1 to 10 carbon atoms. A plurality of R ^d are each independently a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms. In the production method using the olefin polymerization catalyst, the polymer can be produced even at a high temperature as described later. Therefore, benzene-insoluble or sparingly soluble organoaluminumoxy compounds such as those exemplified in JP-A-2-78687 can also be used. In addition, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more alkyl groups described in JP-A-2-24701 and JP-A-3-103407, etc. It can be used preferably.

The above-mentioned "benzene-insoluble or sparingly soluble" organoaluminum oxy compound means that the amount of the compound dissolved in benzene at 60°C is usually 10% by mass or less, preferably 5% by mass or less in terms of Al atoms. , particularly preferably 2% by mass or less, refers to an organoaluminum oxy compound that is insoluble or sparingly soluble in benzene.
The organoaluminumoxy compounds (b-1) exemplified above may be used alone or in combination of two or more.

<<Ionic compound (b-2)>>
The compound (b-2) that reacts with the bridged metallocene compound (A) to form an ion pair (hereinafter also referred to as "ionic compound (b-2)") includes those described in JP-A-1-501950, JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, JP-A-2004-51676, US Patent No. Lewis acids, ionic compounds, borane compounds and carborane compounds described in, for example, No. 5,321,106 are exemplified. Further examples are heteropolycompounds and isopolycompounds. Among these, the compound represented by the general formula [B5] is preferable as the ionic compound (b-2).

式［Ｂ５］において、Ｒ^e+としては、Ｈ⁺、オキソニウムカチオン、カルベニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンが例示される。Ｒ^f、Ｒ^g、Ｒ^hおよびＲⁱはそれぞれ独立に有機基を示し、好ましくはアリール基またはハロゲン置換アリール基を示す。

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

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

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

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

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

1. When R ^e+ is a carbenium cation (carbenium salt)
Carbenium salts include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(3,5-ditrifluoromethylphenyl)borate, tris(4-methylphenyl)carbene Examples include nium tetrakis(pentafluorophenyl)borate and tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate.

2. When R ^{e +} is an ammonium cation (ammonium salt)
Examples of ammonium salts include trialkylammonium salts, N,N-dialkylanilinium salts, and dialkylammonium salts.

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

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

Specific examples of dialkylammonium salts include diisopropylammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.
The ionic compound (b-2) may be used alone or in combination of two or more.

<<organoaluminum compound (b-3)>>
Examples of the organoaluminum compound (b-3) include an organoaluminum compound represented by the general formula [B6] and a complex alkylate of a Group 1 metal of the periodic table and aluminum represented by the general formula [B7]. .

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

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

Examples of the organoaluminum compound [B6] include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum and trioctylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum; tri-branched alkylaluminum such as tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triphenyl triarylaluminum such as aluminum and tritolylaluminum; dialkylaluminum hydride _such as diisopropylaluminum _hydride and diisobutylaluminum hydride _; general formula ( _iC4H9 ) _xAly ( _C5H10 ) _z (wherein x, y and z are positive numbers and z≤2x.) alkenyl aluminum such as isoprenyl aluminum; alkyl aluminum alkoxides such as isobutyl aluminum methoxide and isobutyl aluminum ethoxide; dialkylaluminum alkoxides such ^as _{diethylaluminum} ethoxide _and dibutylaluminum butoxide ^; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and ^{butylaluminum} sesquibutoxide; ^b is synonymous with R ^a and R ^b in formula [B6]. Partially alkoxylated alkylaluminum having an average composition represented by: diethylaluminum phenoxide, diethylaluminum (2,6-di-tert -butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum sesquichloride , ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dihydride , partially hydrogenated alkylaluminum dihydrides such as propylaluminum dihydride; partially alkoxylated and halogenated alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide; Aluminum; is exemplified.

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

As the organoaluminum compound (b-3), trimethylaluminum and triisobutylaluminum are preferred from the standpoint of easy availability. The organic aluminum compound (b-3) may be used alone or in combination of two or more.

<Carrier (C)>
A carrier (C) may be used as a component of the olefin polymerization catalyst. The carrier (C) is an inorganic compound or an organic compound, and is a granular or particulate solid.

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

Porous oxides have different properties depending on the type and manufacturing method, but preferably have a particle size of 10 to 300 μm, more preferably 20 to 200 μm; a specific surface area of preferably 50 to 1000 m ² /g, more preferably is in the range 100-700 m ² /g; the pore volume is preferably in the range 0.3-3.0 cm ³ /g. Such porous oxides are calcined at 100 to 1000° C., preferably 150 to 700° C., if necessary. Examples of inorganic halides include MgCl ₂ , MgBr ₂ , MnCl ₂ and MnBr ₂ . The inorganic halide may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Alternatively, a component obtained by dissolving the inorganic halide in a solvent such as alcohol and then depositing it in the form of fine particles using a precipitating agent can also be used.

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

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

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

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

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

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

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

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

<Structure of Olefin Polymerization Catalyst>
When olefin is polymerized using the olefin polymerization catalyst, the amount of each component that can constitute the olefin polymerization catalyst is as follows. Moreover, in the olefin polymerization catalyst, the content of each component can be set as follows.

(1) When olefins are polymerized using an olefin polymerization catalyst, the amount of the crosslinked metallocene compound (A) is generally 10 ^-9 to 10 ^-1 mol, preferably 10 ^-8 to 10 mol, per liter of reaction volume. It is used in an amount such that it is ^-2 moles.

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

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

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

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

[2] Polymerization method In the production of the 4-methyl-1-pentene copolymer (B), polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Examples of inert hydrocarbon media used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. The inert hydrocarbon medium may be used singly or in combination of two or more. A so-called bulk polymerization method can also be used in which the liquefied olefin itself, which can be supplied to the polymerization, is used as a solvent.

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

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

Hydrogen, in particular, can be said to be a preferable additive because it has the effect of improving the polymerization activity of the catalyst and the effect of increasing or decreasing the molecular weight of the polymer. When hydrogen is added to the system, the appropriate amount is about 0.00001 to 100 NL per mole of olefin. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system can be adjusted by a method of performing a reaction that produces or consumes hydrogen in the system, a method of separating hydrogen using a membrane, a method of It can also be adjusted by discharging the gas out of the system.
The polymer obtained by the production method may be subjected, if necessary, to post-treatment steps such as a catalyst deactivation treatment step, a catalyst residue removal step, and a drying step after being synthesized by the above method.

[4-methyl-1-pentene copolymer composition (X)]
Content ratio of 4-methyl-1-pentene (co)polymer (A) and 4-methyl-1-pentene copolymer (B) in 4-methyl-1-pentene copolymer composition (X) is 5.0 to 95.0 parts by mass of 4-methyl-1-pentene (co)polymer (A), with the total of (co)polymer (A) and copolymer (B) being 100 parts by mass. , preferably 40.0 to 85.0 parts by mass, more preferably 45.0 to 70.0 parts by mass, 4-methyl-1-pentene copolymer (B) is 5.0 to 95.0 parts by mass parts, preferably 15.0 to 60.0 parts by mass, more preferably 30.0 to 55.0 parts by mass.

The total content of 4-methyl-1-pentene (co)polymer (A) and 4-methyl-1-pentene copolymer (B) is 4-methyl-1-pentene copolymer composition (X ) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more of the whole.

When the content of the 4-methyl-1-pentene (co)polymer (A) and the 4-methyl-1-pentene copolymer (B) is within the above range, the requirements (X-1) to (X -3) is preferable for obtaining a fiber that satisfies, and the 4-methyl-1-pentene copolymer composition (X) has high impact resistance while having transparency and rigidity, and further has high heat resistance. It is preferable in that it has

Ethylene and carbon atoms contained in the 4-methyl-1-pentene (co)polymer (A) for all structural units contained in the polymer in the 4-methyl-1-pentene copolymer composition (X) A structural unit derived from at least one olefin selected from the group consisting of α-olefins (excluding 4-methyl-1-pentene) having numbers 3 to 20, and the 4-methyl-1-pentene copolymer (B) The ratio of the total content of structural units derived from at least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) contained in It is preferably 0.5 to 20.0 mol %, more preferably 0.5 to 11.5 mol %.

4-methyl- contained in the 4-methyl-1-pentene (co)polymer (A) for all structural units contained in the polymer in the 4-methyl-1-pentene copolymer composition (X) The ratio of the total content of structural units derived from 1-pentene to structural units derived from 4-methyl-1-pentene contained in the 4-methyl-1-pentene copolymer (B) is 80. It is preferably 0 to 99.5 mol %, more preferably 88.5 to 99.5 mol %.

The 4-methyl-1-pentene copolymer composition (X) preferably has a melt flow rate (MFR) of 5 to 400 g/10 minutes measured at 260° C. under a load of 5 kg according to ASTM D1238. , 5 to 180 g/10 min.
The 4-methyl-1-pentene copolymer composition (X) preferably has a melting point (Tm) of 200 to 240°C, more preferably 225 to 240°C.

The 4-methyl-1-pentene copolymer composition (X) may be 4-methyl-1-pentene (co)polymer (A) and 4 At least one selected from polymers other than the -methyl-1-pentene copolymer (B) and additives for resins may optionally be contained. Hereinafter, other polymers different from 4-methyl-1-pentene (co)polymer (A) and 4-methyl-1-pentene copolymer (B) are also referred to as "other polymers (D)". , the resin additive is also referred to as "additive (C)".

<<Other polymer (D)>>
As the other polymer (D), thermoplastic resins different from the 4-methyl-1-pentene (co)polymer (A) and 4-methyl-1-pentene copolymer (B) of the present invention are widely used. can be used. The content of the other polymer (D) is preferably 30% by mass or less, more preferably 20% by mass or less, and 10% by mass with respect to the total mass of the copolymer composition (X). % or less.

The thermoplastic resin is not particularly limited as long as it is different from the 4-methyl-1-pentene (co)polymer (A) and the 4-methyl-1-pentene copolymer (B),
Thermoplastic polyolefin resins: polyethylene such as low-density, medium-density, high-density polyethylene, high-pressure low-density polyethylene, polypropylene such as isotactic polypropylene and syndiotactic polypropylene, poly-1-butene, poly-4-methyl- 1-pentene, poly 3-methyl-1-pentene, poly 3-methyl-1-butene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α-olefin copolymer , 4-methyl-1-pentene/α-olefin copolymer, cyclic olefin copolymer, chlorinated polyolefin, and modified polyolefin resin obtained by modifying these olefin resins;
Thermoplastic polyamide resins: for example, aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612);
Thermoplastic polyester resin: for example, polyethylene terephthalate, polybutylene terephthalate, polyester elastomer;
Thermoplastic vinyl aromatic resin: for example, polystyrene, ABS resin, AS resin, styrene elastomer (styrene-butadiene-styrene block polymer, styrene-isoprene-styrene block polymer, styrene-isobutylene-styrene block polymer, hydrogenation of these thing);
Thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; vinyl acetate copolymer such as ethylene-vinyl acetate copolymer; ethylene-methacrylic acid acrylate copolymer; ionomer; ethylene-vinyl alcohol copolymer; alcohol; fluororesin; polycarbonate; polyacetal; polyphenylene oxide; polyphenylene sulfide polyimide; polyarylate; polysulfone;
Copolymer rubber: for example, ethylene/α-olefin/diene copolymer, propylene/α-olefin/diene copolymer, 1-butene/α-olefin/diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, silicone rubber;
etc. are exemplified. Among the thermoplastic polyolefin-based resins described above, for example, polyethylene and polypropylene can also be used as a crystal nucleating agent. 5% by mass.

Among thermoplastic resins, preferably low density, medium density, high density polyethylene, high pressure low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 3-methyl-1-pentene, poly 3-methyl-1-butene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α-olefin copolymer, styrene elastomer, vinyl acetate copolymer, ethylene/methacryl Acid acrylate copolymers, ionomers, fluorine resins, rosin resins, terpene resins, and petroleum resins, more preferably polyethylene, isotactic polypropylene, or Syndiotactic polypropylene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α-olefin copolymer, vinyl acetate copolymer, styrene elastomer, rosin resin, terpene resins and petroleum resins.

Part or all of the other polymer (D) may be a graft-modified polymer obtained by graft-modifying a polymer with a polar monomer. The graft modification conforms to <<graft modification>> described above for the 4-methyl-1-pentene (co)polymer (A).
Another polymer (D) may be used individually by 1 type, and may use 2 or more types together.

<<Additive (C)>>
Additives (C) include, for example, nucleating agents, antiblocking agents, pigments, dyes, fillers, lubricants, plasticizers, release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, and surfactants. , antistatic agents, weather stabilizers, heat stabilizers, anti-slip agents, foaming agents, crystallization aids, anti-fogging agents, anti-aging agents, hydrochloric acid absorbers, impact modifiers, cross-linking agents, co-cross-linking agents, cross-linking aids agents, adhesives, softeners, and processing aids.

Additives (C) may be used singly or in combination of two or more.
The content of the additive (C) is not particularly limited depending on the application within a range that does not impair the object of the present invention. It is preferably 0.001 to 30% by mass for each.

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

The amount of the nucleating agent is not particularly limited, but the 4-methyl-1-pentene (co)polymer (A), 4-methyl-1-pentene copolymer (B) and other polymer (D) It is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount. The nucleating agent can be appropriately added during polymerization, after polymerization, or during molding.

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

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

Examples of fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal Examples include oxides (iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powders, mica, and glass flakes.

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

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

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

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

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

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

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

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

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

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

The organic peroxide is 4-methyl-1-pentene (co)polymer (A), 4-methyl-1-pentene copolymer (B) and other polymer (D) with respect to the total amount of 100 parts by mass, It is preferably used in a proportion of 0.05 to 10 parts by mass.

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

By using the above compound, a uniform and moderate cross-linking reaction can be expected. In particular, divinylbenzene is preferably used in the present invention. Divinylbenzene is easy to handle, has good compatibility with polymers, and has the action of solubilizing organic peroxides, and acts as a dispersant for organic peroxides. For this reason, a homogeneous cross-linking effect is obtained, and a dynamically heat-treated product with well-balanced fluidity and physical properties can be obtained.

The cross-linking aid is 4-methyl-1-pentene (co)polymer (A), 4-methyl-1-pentene copolymer (B) and other polymer (D) with respect to the total amount of 100 parts by mass and preferably in a proportion of 0.05 to 10 parts by mass.

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

The amount of softening agent is not particularly limited, but the amount of 4-methyl-1-pentene (co)polymer (A), 4-methyl-1-pentene copolymer (B) and other polymer (D) The amount is preferably 1 to 200 parts by mass with respect to the total amount of 100 parts by mass. The softener facilitates processing and helps disperse carbon black and the like when preparing the copolymer composition (X).

[Method for producing 4-methyl-1-pentene copolymer composition (X)]
Although the method for producing the 4-methyl-1-pentene copolymer composition (X) is not particularly limited, for example, 4-methyl-1-pentene (co)polymer (A), 4-methyl-1-pentene The polymer (B) and, if necessary, other optional components are mixed in the above addition ratio, and then melt-kneaded to obtain the mixture.

The melt-kneading method is not particularly limited, and can be carried out using a generally commercially available melt-kneading device such as an extruder.
For example, the cylinder temperature of the part where kneading is performed by a kneader is usually 220 to 320°C, preferably 250 to 300°C. If the temperature is lower than 220°C, kneading becomes insufficient due to insufficient melting, and it is difficult to see improvement in the physical properties of the copolymer composition. On the other hand, if the temperature is higher than 320° C., thermal decomposition of components such as the 4-methyl-1-pentene (co)polymer (A) and the 4-methyl-1-pentene copolymer (B) may occur. be. The kneading time is usually 0.1 to 30 minutes, preferably 0.5 to 5 minutes. If the kneading time is less than 0.1 minute, sufficient melt-kneading is not performed, and if the kneading time exceeds 30 minutes, 4-methyl-1-pentene (co)polymer (A) and 4-methyl-1 - Thermal decomposition of components such as the pentene copolymer (B) may occur.

[fiber]
Fibers containing the 4-methyl-1-pentene copolymer or 4-methyl-1-pentene copolymer composition (X) of the present invention include, for example, the 4-methyl-1-pentene-based polymer described above. Monofilaments, multifilaments, flat yarns, cut fibers, and non-woven fabrics can be produced by extruding a melted resin composition through a spinneret.

The melting temperature in the melt spinning process when manufacturing monofilaments, multifilaments, and flat yarns can be appropriately selected according to the melting point of the 4-methyl-1-pentene polymer, but is in the range of 250 to 320°C. is preferable, and a more preferable range is 270 to 310°C. When the melting temperature is within the above range, excessive thermal decomposition of the 4-methyl-1-pentene polymer can be suppressed, and the elongational viscosity of the fibrous strand extruded from the die is sufficiently lowered, so that mechanical A fiber having excellent strength and good spinnability can be obtained.

The fibers thus obtained may be drawn further. The degree of stretching is, for example, such that the 4-methyl-1-pentene polymer is effectively given at least uniaxial molecular orientation, so that the elastic modulus and strength can be improved. The draw ratio is usually in the range of 1.05 to 10.0 times, more preferably 1.1 to 7.0 times, still more preferably 1.2 to 6.0 times.

The drawing temperature in the above drawing operation can be appropriately selected according to the glass transition temperature and melting point of the 4-methyl-1-pentene polymer, or the strength and elongation of the fiber obtained after drawing. It is preferably 35 to 200°C, more preferably 40 to 180°C. When the drawing temperature is within the above range, yarn breakage is suppressed, and fibers can be stably obtained.

When the above stretching operation is carried out, it may be a one-stage stretching method or a multi-stage stretching method comprising two or more stages.
Using the fibers obtained by the above method, a nonwoven fabric can be produced by a wet papermaking method, a sintering method, a needle punching method, a carding method, a cross layer method, a random waver method, an air forming method, or the like.

In the case of manufacturing a nonwoven fabric composed of single-layer fibers, it can be carried out according to a method such as a spunbond method, a meltblown method, a card method, or the like.
Since the fibers of the present invention can be made ultrafine, they are suitable for various applications such as filters, masks, battery separators, heat insulating materials, etc., which are made of non-woven fabric having a dense structure.

The cross-sectional shape of the fiber of the present invention is not particularly limited, and may be a perfect circular cross-section or a non-circular, so-called irregular cross-section. The modified cross section includes a polygonal shape, an elliptical shape, a flat shape, a multi-leaf shape having many branches on the fiber surface (specifically, a multi-leaf shape with 3 to 32 lobes), and a star shape. Shapes include C-shapes, H-shapes, S-shapes, T-shapes, Y-shapes, W-shapes, and I-shapes.

Furthermore, the fiber of the present invention may be a solid fiber having no longitudinally continuous hollow portion in the cross section of the fiber, or a hollow fiber having at least one longitudinally continuous hollow portion. may

[Fibrous structure]
Since the fibers of the present invention have a low elongation, they are less likely to break and have less fluff. This characteristic can be used to obtain useful fibrous structures containing the fibers of the present invention.

The fibers of the present invention can be used in the form of monofilaments, multifilaments, flat yarns, ropes, curing nets, fishing nets, fishing lines, life jackets, insect nets, women's clothing, men's clothing, linings, underwear, down jackets, vests, etc. Sports such as windbreakers, socks, insoles, masks, surgical gowns, release cloths, oil absorbent cloths, waterproof cloths, outdoor wear, supporters, bandages, fabrics for sleeping bags, fabrics for tents, ski wear, golf wear, swimwear, etc. Wear, artificial turf, filling for futon, lining for futon, duvet cover, blanket, lining for blanket, blanket cover, sheets, filling for pillow, pillow cover, filling for plush toys, disposable diapers, sanitary products, sanitary products, sewing thread, Filters, bag filters, dust collection filters, air cleaners, hollow fiber filters, water purification filters, gas separation membranes, dental floss, toothbrushes, brushes, wigs, belts, bags, shoes, table cloths, curtains, carpets, car mats, It is suitable for applications such as belt conveyor base fabrics, optical fibers, sound absorbing materials, and heat insulating materials, but the applications are not limited to these.

In addition to being lightweight and having high strength, the fibers of the present invention can be made into ultrafine fibers. , Futon lining, Duvet cover, Blanket, Blanket lining, Blanket cover, Sheets, Pillow filling, Pillow cover, Stuffed toy filling, Non-woven fabric, Disposable diapers, Sanitary products, Sanitary products, Sewing threads, Filters, Bag filters, Collections It is suitable for applications such as dust filters, air cleaners, hollow fiber filters, water purification filters, gas separation membranes, battery separator films, sound absorbing materials, and heat insulating materials, but the applications are not limited thereto.

Methods for measuring physical properties in the following examples and comparative examples are shown below.
[Single yarn fineness]
In an environment of a temperature of 20° C. and a humidity of 65% RH, 100 m of fiber was weighed using an INTEC electric measuring machine. The mass of the obtained skein was measured, and the fineness (dtex) was calculated using the following formula. The measurement was performed 5 times per sample, and the average value was taken as the total fineness.
Total fineness (dtex) = Mass (g) of 100m of fiber x 100
The obtained fineness value was divided by the number of filaments of the fiber, and the resulting value was defined as the single filament fineness.

[Breaking strength, elongation]
The strength and elongation were calculated according to JIS L1013:1999 (chemical fiber filament yarn test method) 8.5 using the polymethylpentene fiber obtained in the example as a sample. Using Autograph AG-50NISMS manufactured by Shimadzu Corporation, a tensile test was performed under the conditions of an initial sample length of 20 cm and a tensile speed of 20 cm/min in an environment of a temperature of 20° C. and a humidity of 65% RH. Breaking strength (cN/dtex) is calculated by dividing the stress (cN) at the point indicating the maximum load by the fineness (dtex), and the elongation (L1) at the point indicating the maximum load and the initial sample length (L0) are used. Elongation (%) was calculated by the following formula. The measurement was performed 10 times per sample, and the average value was used as the strength and elongation.
Elongation (%) = {(L1-L0)/L0} x 100

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

[Melt flow rate]
Melt flow rate (MFR) was measured according to ASTM D1238 at 260°C under a 5 kg load.

[Synthesis of transition metal complex]
According to Synthesis Example 4 of WO 2014/050817, (8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6, 7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride was synthesized. This compound is also described as "metallocene compound (a)".

[Production Example 1] 4-methyl-1-pentene/1-hexadecene/1-octadecene copolymer (A1)
A magnetic stirrer was placed in a sufficiently dried and nitrogen-substituted Schlenk tube, 5.0 μmol of the metallocene compound (a) was added, and 300 eq/cat. of modified methylaluminoxane suspension was added. (n-hexane solvent, 1.50 mmol in terms of aluminum atom) was added with stirring at 23° C., 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.

500 mL of 4-methyl-1-pentene, 250 mL of cyclohexane, and 10 mL of Linearene 168 (manufactured by Idemitsu Kosan Co., Ltd.) (a mixture of 1-hexadecene and 1-octadecene) are placed in a sufficiently dried and nitrogen-substituted 1,500-mL SUS autoclave. and 0.5 mmol of a hexane solution of triisobutylaluminum (aluminum concentration: 0.5 mol/L), and after adding 124.3 mL of hydrogen, the temperature was raised to a polymerization temperature of 60°C while stirring at 850 rpm. .

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

The polymerization liquid taken out from the cooled/depressurized autoclave was put into a 1:1 solution of acetone and methanol to precipitate the polymer, which was collected by filtration. After that, 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 (A1).

Table 1 shows the results of measuring the melting point (Tm) and melt flow rate (MFR) of the obtained copolymer (A1). "Comonomer" in Table 1 refers to ethylene and α-olefins of 3 to 20 carbon atoms (except 4-methyl-1-pentene).

[Production Examples 2, 3, 7 to 11] 4-methyl-1-pentene/1-hexadecene/1-octadecene copolymers (A2), (A3), (A7), (B1) to (B4)
The procedure was the same as in Production Example 1, except that the charging amounts of 4-methyl-1-pentene and linearene 168 were changed so that the contents of 1-hexadecene and 1-octadecene were the numerical values shown in Table 1 or Table 2. 4-methyl-1-pentene/1-hexadecene/1-octadecene copolymers (A2), (A3), (A7) and (B1) to (B4) were obtained.

In the same manner as in Production Example 1, the melting points (Tm) and melt flow rates (MFR) of the copolymers (A2), (A3) and (A7) were measured. Table 2 shows the results of measuring the melting point (Tm) and melt flow rate (MFR) of B4).

[Production Examples 4-6] 4-methyl-1-pentene/1-decene copolymers (A4) to (A6)
In Comparative Example 7 of International Publication No. 2006/054613, by changing the ratio of 4-methyl-1-pentene and 1-decene so that the content of 1-decene is the numerical value shown in Table 1 , 4-methyl-1-pentene/1-decene copolymers (A4) to (A6) were obtained.
Table 1 shows the results of measuring the melting points (Tm) and melt flow rates (MFR) of the copolymers (A4) to (A6) in the same manner as in Production Example 1.

[Production Example 12] 4-methyl-1-pentene/1-hexene copolymer (B'1)
A magnetic stirrer was placed in a sufficiently dried and nitrogen-substituted Schlenk tube, 5.0 μmol of the metallocene compound (a) was added, and 300 eq/cat. of modified methylaluminoxane suspension was added. (n-hexane solvent, 1.50 mmol in terms of aluminum atom) was added with stirring at 23° C., 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.

350 mL of 4-methyl-1-pentene, 250 mL of cyclohexane, 250 mL of 1-hexene and a hexane solution of triisobutyl aluminum (aluminum concentration: 0.5 mol/L ) was charged, 71.0 mL of hydrogen was added, and the temperature was raised to a polymerization temperature of 60° C. while stirring at 850 rpm.

The autoclave was charged with 0.1 mL of the catalyst solution (concentration of metallocene compound (a): 0.1 μmol) to initiate polymerization, and 30 minutes after the initiation, methanol was added to terminate the polymerization.

The polymerization liquid taken out from the cooled/depressurized autoclave was put into a 1:1 solution of acetone and methanol to precipitate the polymer, which was collected by filtration. Thereafter, the recovered polymer was dried under reduced pressure at 80° C. for 12 hours to obtain a 4-methyl-1-pentene/1-hexene copolymer (B'1).
Table 2 shows the results of measuring the melting point (Tm) and melt flow rate (MFR) of the copolymer (B'1) in the same manner as in Production Example 1.

[Examples 1 to 4]
4-methyl-1-pentene copolymer composition (X ).
The obtained 4-methyl-1-pentene copolymer (X) is subjected to a capillary rheometer (capilograph 1B, barrel diameter 10 mmφ) manufactured by Toyo Seiki Co., Ltd., and a hole diameter of 1 mm ( The molten polymer was extruded at a cylinder speed of 10 mm/min through a nozzle having one hole (circular), and the spun yarn was cooled at 23° C. and wound at a winding speed of 10 m/min to obtain an undrawn yarn. Next, using a heating drawing machine (manufactured by Imoto Seisakusho Co., Ltd.), drawing was performed at a drawing ratio of 3.0 times at a feeding line speed of 0.2 m / min and a drawing temperature of 95 to 100 ° C. to obtain a drawn yarn. .
The elongation, breaking strength and single filament fineness of the obtained drawn yarn were measured by the above measuring methods. Table 3 shows the measurement results.

[Comparative Example 1]
The above copolymer (A4) and copolymer (B'1) were mixed at the ratio shown in Table 3 to obtain a 4-methyl-1-pentene copolymer composition.
A drawn yarn was obtained in the same manner as in Example 1 using the obtained 4-methyl-1-pentene copolymer composition.
The elongation, breaking strength and single filament fineness of the obtained drawn yarn were measured by the above measuring methods. Table 3 shows the measurement results.

[Comparative Examples 2 to 4]
Drawn yarns were obtained in the same manner as in Example 1 using the above copolymers (A5) to (A7).
The elongation, breaking strength and single filament fineness of the obtained drawn yarn were measured by the above measuring methods. Table 3 shows the measurement results.

Claims (4)

5.0 to 95.0 parts by mass of a 4-methyl-1-pentene (co)polymer (A) satisfying the following requirements (Aa) and (Ab);
5.0 to 95.0 parts by mass of 4-methyl-1-pentene copolymer (B) satisfying the following requirements (Ba) and (Bb) (provided that (co)polymer (A) and The total with the polymer (B) is 100 parts by mass)
A 4-methyl-1-pentene copolymer composition (X) containing
Fibers that satisfy the following requirements (X-1) to (X-3).
(Aa) the content (U1) of structural units derived from 4-methyl-1-pentene is 96.0 mol% or more and 100 mol% or less;
The content (U2) of structural units derived from at least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 mol% or more4 0 mol % or less (provided that the total of (U1) and (U2) is 100 mol %).
(Ab) Melting point (Tm) measured by DSC is 200 to 240°C.
(Ba) the content (U3) of structural units derived from 4-methyl-1-pentene is 73.0 mol% or more and less than 96.0 mol%;
The content (U4) of structural units derived from at least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 4.0 mol% 27.0 mol % or less (provided that the total of (U3) and (U4) is 100 mol %).
(Bb) Melting point (Tm) measured by DSC is less than 230° C., or no peak indicating melting point appears in DSC measurement.
(X-1) Elongation is 50 to 300%.
(X-2) Breaking strength is 2.0 to 7.0 cN/dtex.
(X-3) Single filament fineness is 0.5 to 1200 dtex. Ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl -1-pentene) is at least one α - olefin structural unit selected from α-olefins having 10 to 20 carbon atoms. fiber. For all structural units contained in the polymer in the copolymer composition (X),
At least one selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) contained in the 4-methyl-1-pentene (co)polymer (A) a structural unit derived from an olefin of
At least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) contained in the 4-methyl-1-pentene copolymer (B) The fiber according to claim 1 or 2 , wherein the ratio of the total content of structural units derived from is 0.5 to 20.0 mol%. A fiber structure at least partially comprising the fiber according to any one of claims 1 to 3 .