JP6920084B2 - 4-Methyl-1-pentene copolymer composition - Google Patents

Description

The present invention relates to a 4-methyl-1-pentene copolymer composition having specific physical properties.

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 and 2).

WO2005 / 121192A1 Japanese Unexamined Patent Publication No. 2008-14145

A molded product made from a 4-methyl-1-pentene polymer may not have sufficient impact resistance, and it is required to improve the impact resistance. On the other hand, in various applications in which 4-methyl-1-pentene-based polymers are used, the molded product is often required to have transparency and rigidity. However, a 4-methyl-1-pentene polymer having high impact resistance while maintaining transparency and rigidity has not been found so far. Furthermore, high heat resistance is also required for the purpose of sterilization and the like.
An object of the present invention is to provide a 4-methyl-1-pentene copolymer composition having high impact resistance while having transparency and rigidity, and further having high heat resistance.

The present inventors have made diligent studies to solve the above problems. As a result, they have found that a 4-methyl-1-pentene copolymer composition having a specific composition and a specific property can solve the above-mentioned problems, and have completed the present invention.

The present invention relates to the following [1] to [3].
[1] 50.0 to 95.0 parts by mass of 4-methyl-1-pentene (co) polymer (A) satisfying the following requirements (A-a) to (A-c) and the following requirements (B-a). ) To (B) -satisfying 4-methyl-1-pentene copolymer (B) 5.0 to 50.0 parts by mass (however, the total of (A) and (B) is 100 parts by mass). 4-Methyl-1-pentene copolymer composition (X) containing.

(A-a) The content (U1) of the structural unit derived from 4-methyl-1-pentene is 100 to 90.0 mol%, and ethylene and α-olefin (4-methyl) having 3 to 20 carbon atoms. The content (U2) of the structural unit derived from the olefin selected from the group consisting of -1-pentene) is 0 to 10.0 mol%.
(A-b) The ultimate viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.0 dl / g.
(Ac) The melting point (Tm) measured by DSC is in the range of 200 to 260 ° C.

(BA) The content (U3) of the structural unit derived from 4-methyl-1-pentene is 20.0 to 95.0 mol%, and ethylene and α-olefin (4) having 3 to 20 carbon atoms. The content (U4) of the structural unit derived from −methyl-1-pentene) is 5.0 to 80.0 mol%.
(Bb) The ultimate viscosity [η] measured in 135 ° C. decalin is 0.5 to 5.0 dl / g.
(B-c) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is 1.0 to 3.5. be.
(Bd) The melting point (Tm) measured by DSC is in the range of less than 200 ° C., or the peak indicating the melting point does not appear in the DSC measurement.
(B-e) In the dynamic viscoelasticity measurement in the temperature range of -30 to 240 ° C. at a frequency of 10 rad / s, the temperature (Tg) at which tan δ is the maximum value in the temperature range of -30 ° C. to 50 ° C. is 14. It is below 0.0 ° C.

[2] The 4-methyl-1-pentene copolymer composition (X) according to [1], which satisfies the following requirements (X-1) to (X-3).
(X-1) The tensile elastic modulus measured according to JIS K7113 is 400 MPa or more.
(X-2) The Izod impact strength at 23 ° C. measured according to ASTM D256 is 50 J / m or more.
(X-3) The Vicat softening temperature measured according to ASTM D1525 is 100 ° C. or higher.

[3] A molded product containing the 4-methyl-1-pentene copolymer composition (X) according to [1] or [2].

According to the present invention, it is possible to provide a 4-methyl-1-pentene copolymer composition having high impact resistance while having transparency and rigidity, and further having high heat resistance.

FIG. 1 is a diagram in which the IZOD impact strength is plotted against the tensile elastic modulus of the compositions obtained in Examples and Comparative Examples.

Hereinafter, the 4-methyl-1-pentene copolymer composition of the present invention and a molded product containing the same will be described in detail, including suitable embodiments.
[4-Methyl-1-pentene copolymer composition (X)]
The 4-methyl-1-pentene copolymer composition (X) of the present invention is a 4-methyl-1-pentene (co) polymer (A) that satisfies the requirements (A-a) to (A-c) described later. ) 50.0 to 95.0 parts by mass and 5.0 to 50.0 parts by mass of the 4-methyl-1-pentene copolymer (B) satisfying the requirements (B-a) to (B-e) described later. (However, the total of (A) and (B) is 100 parts by mass).

Ratio of contents of 4-methyl-1-pentene (co) copolymer (A) and 4-methyl-1-pentene copolymer (B) in 4-methyl-1-pentene copolymer composition (X) The 4-methyl-1-pentene (co) copolymer (A) is preferably 50.0 to 90.0 parts by mass, more preferably 50 parts by mass, with the total of (A) and (B) being 100 parts by mass. 0 to 80.0 parts by mass, more preferably 60.0 to 80.0 parts by mass, and 4-methyl-1-pentene copolymer (B) is preferably 10.0 to 50.0 parts by mass. It is preferably 20.0 to 50.0 parts by mass, and more preferably 20.0 to 40.0 parts by mass. The total content of 4-methyl-1-pentene (co) polymer (A) and 4-methyl-1-pentene copolymer (B) is the 4-methyl-1-pentene copolymer composition (X). ) It is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more with respect to the whole.

When the contents of the 4-methyl-1-pentene (co) polymer (A) and the 4-methyl-1-pentene copolymer (B) are within the above range, the 4-methyl-1-pentene copolymer The composition (X) is preferable in that it has high impact resistance while having transparency and rigidity, and further has high heat resistance.

Further, the 4-methyl-1-pentene copolymer composition (X) of the present invention preferably satisfies the following requirements (X-1) to (X-3), and further satisfies the following requirements (X-4). It is preferable to satisfy. Each requirement will be described below.

<< Requirements (X-1) >>
The tensile elastic modulus measured according to JIS K7113 is 400 MPa or more. The tensile elastic modulus is preferably 500 MPa or more. Rigidity is excellent when it is at least the above lower limit value. The upper limit is usually 1800 MPa or less, preferably 1500 MPa or less.

<< Requirements (X-2) >>
The Izod impact strength (with rear notch) at 23 ° C. measured according to ASTM D256 is 50 J / m or more. The Izod impact strength is preferably 100 J / m or more, more preferably 200 J / m or more.

<< Requirements (X-3) >>
The Vicat softening temperature measured according to ASTM D1525 is 100 ° C. or higher. When the Vicat softening temperature is 100 ° C. or higher, a molded product having excellent heat resistance can be obtained. The Vicat softening temperature is preferably 110 ° C. or higher, more preferably 120 ° C. or higher.

<< Requirements (X-4) >>
The internal haze is 20% or less. When the internal haze is 20% or less, the transparency of the copolymer composition (X) is good. The internal haze is preferably 15% or less, more preferably 10% or less.

[4-Methyl-1-pentene (co) polymer (A)]
The 4-methyl-1-pentene (co) polymer (A) satisfies the following requirements (Aa) to (Ac). Each requirement will be described below.

<< Requirements (A-a) >>
The requirement (A-a) is that the 4-methyl-1-pentene (co) polymer (A) of the present invention has a content (U1) of a structural unit derived from 4-methyl-1-pentene of 100 to 90. The content (U2) of the structural unit derived from an 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%. It is ~ 10.0 mol%.

The 4-methyl-1-pentene (co) polymer (A) has, for example, a homopolymer of 4-methyl-1-pentene (that is, a content of a structural unit derived from 4-methyl-1-pentene of 100 mol). %), And a copolymer of 4-methyl-1-pentene and other olefins.

Here, from the viewpoint of transparency and heat resistance, the content of the structural unit derived from 4-methyl-1-pentene with respect to all the structural units contained in the 4-methyl-1-pentene (co) polymer (A) ( U1) is preferably from 92.0 to 100 mol%, more preferably from 95.0 to 100 mol%, from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene). The content (U2) of the structural unit derived from at least one selected is preferably 0 to 8.0 mol%, more preferably 0 to 5.0 mol%.

When 4-methyl-1-pentene (co) polymer (A) is a copolymer, it is specifically as ethylene that copolymerizes with 4-methyl-1-pentene and α-olefin having 3 to 20 carbon atoms. , Ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1- Penten, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1- Examples thereof include tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Of these, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, are preferred. They are 1-hexadecene and 1-octadecene, and these α-olefins may be used alone or in combination of two or more.

In the present invention, a structural unit derived from 4-methyl-1-pentene in 4-methyl-1-pentene (co) polymer (A), and ethylene and an α-olefin having 3 to 20 carbon atoms (4). The amount of structural units derived from -methyl-1-pentene) is 4-methyl-1-pentene added during the polymerization reaction, as well as ethylene and α-olefins with 3 to 20 carbon atoms (4-methyl). It can be adjusted by the amount of -1-) (excluding penten).

The 4-methyl-1-pentene (co) polymer (A) may have a structural unit derived from a monomer other than ethylene and an α-olefin having 3 to 20 carbon atoms, as long as the requirements described later are satisfied. The upper limit of the content of the constituent units derived from other monomers is, for example, 10 wt% or less, preferably 5 wt% or less, based on 100 wt% of the total of (U1) and (U2).

<< Requirements (A-b) >>
The requirement (A-b) is that the intrinsic viscosity [η] of 4-methyl-1-pentene (co) polymer (A) measured in decalin at 135 ° C. is in the range of 0.5 to 5.0 dl / g. That is. The ultimate viscosity [η] is preferably 0.7 to 5.0 dl / g, more preferably 0.7 to 4.5 dl / g, and even more preferably 1.0 to 4.0 dl / g. When the ultimate viscosity [η] is within the above range, it is preferable in terms of resin fluidity during molding of the 4-methyl-1-pentene copolymer composition.

The ultimate viscosity [η] can be adjusted within the above range by appropriately selecting the hydrogen concentration and pressure of the polymerization system, and 4-methyl-1-pentene polymers having different ultimate viscosities [η] are mixed. It may be adjusted within the above range.

<< Requirements (Ac) >>
The requirement (A-c) is that the melting point (Tm) of the 4-methyl-1-pentene (co) polymer (A) measured by DSC is in the range of 200 to 260 ° C. The melting point (Tm) is 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 200 to 250 ° C, more preferably 205 to 250 ° C, and even more preferably 210 to 245 ° C. The melting point (Tm) can be arbitrarily adjusted by appropriately selecting the comonomer species and the amount thereof. 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) may be a graft-modified (co) polymer obtained by graft-modifying the (co) polymer with a polar monomer as long as the above requirements are satisfied. good.

[Method for producing 4-methyl-1-pentene (co) polymer (A)]
As a 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 and the like can be adopted. In the method for producing the 4-methyl-1-pentene (co) polymer (A), a conventionally known polymerization catalyst can be used.

When the 4-methyl-1-pentene (co) polymer (A) is a graft-modified (co) polymer, the 4-methyl-1-pentene (co) polymer (A) is subjected to the following graft modification conditions. Can be manufactured.

《Graft denaturation》
Examples of the polar 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, an unsaturated carboxylic acid or a derivative thereof. , Vinyl ester compounds, vinyl chloride, carbodiimide compounds. In particular, unsaturated carboxylic acids or derivatives thereof are preferred. Examples of the unsaturated carboxylic acid or a derivative thereof include an unsaturated compound having one or more carboxylic acid groups, an ester of a compound having a carboxylic acid group and an alkyl alcohol, and an unsaturated compound having one or more anhydrous carboxylic acid groups. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group.

Specific examples of the polar monomer include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid [trademark] (endosis-bicyclo [2.2.1]. ] An unsaturated carboxylic acid such as hepto-5-ene-2,3-dicarboxylic acid) and a derivative of the unsaturated carboxylic acid include, for example, acid halides, amides, imides, anhydrides and esters. Specific examples of such derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate.

These unsaturated carboxylic acids and / or derivatives thereof may be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferable.

The modification is obtained by graft-polymerizing a polar monomer on the (co) polymer which is the modified product. When the polar monomer is graft-polymerized on the modified product, the polar monomer is usually used in an amount of 1 to 100 parts by mass, preferably 5 to 80 parts by mass with respect to 100 parts by mass of the modified product. This graft polymerization is usually carried out in the presence of a radical initiator.

As the radical initiator, an organic peroxide, an azo compound and the like can be used.
The radical initiator can be used as it is by mixing it with the modified product and the polar monomer, or it can be used after being dissolved in a small amount of an organic solvent. The organic solvent can be used without particular limitation as long as it is an organic solvent capable of dissolving the radical initiator.

When the polar monomer is graft-polymerized on the modified product, a reducing substance may be used. When a reducing substance is used, the amount of grafted polar monomer can be improved.
The graft modification of the modified product with the polar monomer can be carried out by a conventionally known method. For example, the modified product is dissolved in an organic solvent, and then the polar monomer and the radical initiator are added to the solution, and the temperature is usually 70 to 200 ° C. It can be carried out by reacting at a temperature of 80 to 190 ° C., usually for 0.5 to 15 hours, preferably 1 to 10 hours.

A modified product (X) containing a modified product, that is, a 4-methyl-1-pentene (co) polymer (A), is produced by reacting the modified product with a polar monomer using an extruder or the like. You can also do it. This reaction is usually carried out above the melting point of the modified product. Specifically, when modifying a thermoplastic resin, for example, it is usually carried out at 120 to 300 ° C., usually for 0.5 to 10 minutes, preferably at a temperature of 160 to 300 ° C., more preferably 180 ° C. to 250 ° C. Will be done.

The amount of modification of the modified product thus obtained (the amount of graft of the polar monomer) is usually 0.1 to 50% by mass, preferably 0.2 to 30% by mass, when the modified product is 100% by mass. More preferably, it is 0.2 to 10% by mass.

Further, the copolymer composition (X) contains a polar monomer, and the 4-methyl-1-pentene (co) polymer (A) contained in the copolymer composition (X) is modified. , To obtain a copolymer composition (X) containing 4-methyl-1-pentene (co) polymer (A) obtained by modifying the 4-methyl-1-pentene (co) polymer (A). You can also do it. The content of the polar monomer is not particularly limited, but is preferably 0.001 to 50% by mass, more preferably 0.001 to 10% by mass, still more preferably 0.001 to 10% by mass, based on 100% by mass of the copolymer composition (X). Is 0.001 to 5% by mass, most preferably 0.01 to 3% by mass. The content of the polar monomer can be easily determined according to the purpose, for example, by appropriately selecting the graft conditions.

Further, the 4-methyl-1-pentene (co) polymer (A) is a (co) polymer (A) obtained by graft-modifying the modified product with a silane coupling agent. May be good. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltricrolsilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N. -(2-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glysidoxypropylmethyldiethoxysilane 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3- (Triethoxysilyl) -1-propaneamine, N, N'-bis (3- (trimethoxysilyl) propyl) ethylenediamine, polyoxyethylenepropyltrialkoxysilane, polyethoxydimethylsiloxane, p-styryltrimethoxysilane, 3 -Acryloxypropyltrimethoxysilane can be mentioned.

When cross-linking with a silane coupling agent, either a dry treatment method or a wet (slurry method) treatment method may be used. Since the 4-methyl-1-pentene (co) polymer (A), which is a water-crosslinked polymer using a silane coupling agent, has a uniform cross-linked state, this (co) polymer (A) The copolymer composition (X) containing the above is suitably used for applications requiring strength and durability such as industrial electric wires and pipes.

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 wettability of the obtained molded product surface is improved. There is. Further, by using the modified product, it may be possible to add compatibility or adhesiveness with a material other than the resin (glass, metal, wood, etc.).

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

[4-Methyl-1-pentene copolymer (B)]
The 4-methyl-1-pentene copolymer (B) satisfies the following requirements (B-a) to (B-e). When the 4-methyl-1-pentene copolymer (B) is a blend polymer, the blend polymer satisfies the following requirements (B-a) to (B-e). Each requirement will be described below.

<< Requirements (BA) >>
The 4-methyl-1-pentene copolymer (B) has a content (U3) of a structural unit derived from 4-methyl-1-pentene of 20.0 to 95.0 mol%, and has ethylene and carbon atoms. The content (U4) of the structural unit derived from the α-olefin (excluding 4-methyl-1-pentene) of the number 3 to 20 is 5.0 to 80.0 mol%.

In the present invention, "ethylene" and "α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene)" are also referred to as "comonomer". The structural unit derived from the comonomer may be a structural unit derived from one type of comonomer, or may be a structural unit derived from two or more types of comonomer.

When (U3) and (U4) are in the above range, it is preferable that the obtained composition exhibits high impact resistance.
The 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, the content of each olefin (for example, 4-methyl-1-pentene, ethylene, carbon number 3) added during the polymerization reaction. It can be adjusted by the amount of α-olefin (α-olefin other than 4-methyl-1-pentene) of ~ 20.

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-pentene, 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 methyl-1-pentene having 6 to 20 carbon atoms are more preferable, and for example, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1- Dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene can be mentioned.

Among them, 1-hexene, 1-hexadecene and 1-octadecene are particularly preferable.
One type of comonomer may be used alone, or two or more types may be used in combination.

The 4-methyl-1-pentene copolymer (B) may have a structural unit derived from other monomers other than ethylene and α-olefin having 3 to 20 carbon atoms as long as the requirements described later are satisfied. .. The upper limit of the content of the constituent units derived from other monomers is, for example, 10 wt% or less, preferably 5 wt% or less, based on 100 wt% of the total of (U3) and (U4).

<< Requirements (B-b) >>
The requirement (B-b) is that the intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (B) measured in decalin at 135 ° C. is in the range of 0.5 to 5.0 dl / g. Is. The ultimate viscosity [η] is preferably 0.7 to 5.0 dl / g, more preferably 0.7 to 4.5 dl / g, still more preferably 1.0 to 4.0 dl / g, and particularly preferably 1. It is 0 to 3.0 dl / g. When the ultimate viscosity [η] is within the above range, the 4-methyl-1-pentene copolymer composition is excellent in moldability and flexibility.

The ultimate viscosity [η] can be adjusted within the above range by appropriately selecting the hydrogen concentration and pressure of the polymerization system, and 4-methyl-1-pentene polymers having different ultimate viscosities [η] are mixed. It may be adjusted within the above range.

<< Requirements (BC) >>
The requirement (B-c) is the ratio of the 4-methyl-1-pentene copolymer (B) to the standard polystyrene-equivalent weight average molecular weight to the number average molecular weight measured by gel permeation chromatography (GPC). Mw / Mn) is in the range of 1.0 to 3.5. Mw / Mn is preferably 1.2 to 3.5, more preferably 1.5 to 3.0, and even more preferably 1.5 to 2.5. When Mw / Mn is large, the composition distribution and the amount of low molecular weight components increase, which may impair the mechanical properties, moldability, and impact resistance of the copolymer composition. When Mw / Mn is within the above range, a molded product having good impact resistance can be obtained from the 4-methyl-1-pentene copolymer composition. Mw / Mn can be adjusted by appropriately selecting a catalyst for olefin polymerization, which will be described later. When it is desired to obtain a polymer having a large Mw / Mn, a multi-stage polymerization method, a mixed catalyst polymerization method, or a method such as mixing 4-methyl-1-pentene polymers having different molecular weights is used as necessary. Can be adjusted.

<< Requirements (B-d) >>
The requirement (Bd) is that the melting point (Tm) of 4-methyl-1-pentene copolymer (B) measured by DSC is in the range of less than 200 ° C., or a peak indicating the melting point appears in the DSC measurement. Do not do it. The melting point (Tm) is 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 160 ° C. or does not show a peak indicating the melting point in DSC measurement, and has a melting point (Tm) of less than 155 ° C. Or, it is more preferable that the peak indicating the melting point does not appear in the DSC measurement.

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

<< Requirements (B-e) >>
In the dynamic viscoelasticity measurement of 4-methyl-1-pentene copolymer (B) at a frequency of 10 rad / s in the temperature range of -30 to 240 ° C, tan δ is the maximum in the temperature range of -30 ° C to 50 ° C. The value temperature (Tg) is 14.0 ° C. or lower. The temperature at which tan δ becomes the maximum value (Tg) corresponds to the glass transition temperature of the 4-methyl-1-pentene copolymer (B). It is preferably 12.0 ° C. or lower, more preferably 10.0 ° C. or lower. The lower limit is not particularly limited, but is usually −30 ° C. or higher, preferably −10 ° C. or higher.

The temperature (Tg) at which tan δ becomes the maximum value can be arbitrarily adjusted by appropriately selecting the comonomer species and the amount thereof. By using the α-olefin listed as the more preferable α-olefin in the requirement (BA) as the comonomer, it is easy to adjust to the above range. When the temperature (Tg) at which tan δ becomes the maximum value is within the above range, the obtained copolymer composition (X) preferably exhibits impact resistance.

Further, the maximum value of tan δ is preferably larger than 0.2, more preferably larger than 0.3, further preferably larger than 0.35, and particularly preferably larger than 0.4.
The 4-methyl-1-pentene copolymer (B) may be a graft-modified copolymer obtained by graft-modifying the copolymer with a polar monomer as long as the above requirements are satisfied. When the 4-methyl-1-pentene copolymer (B) is a graft-modified copolymer, the graft modification is the above-mentioned << graft modification shown for the 4-methyl-1-pentene (co) polymer (A). 》.

[Method for Producing 4-Methyl-1-pentene Copolymer (B)]
The 4-methyl-1-pentene copolymer (B) contains 4-methyl-1-pentene, ethylene, and an α-olefin (4-methyl-) having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst described later. It can be obtained by copolymerizing with at least one olefin selected from 1-pentene).

[1] Olefin polymerization catalyst As an olefin polymerization catalyst,
(A) Cross-linked metallocene compound and
(B) (b-1) Organoaluminium oxy 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 preferable.

<Cross-linked metallocene compound (A)>
The crosslinked metallocene compound (A) is preferably a compound represented by the general formula [A1], and more preferably a compound represented by the 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 the formula [A1], M is a Group 4 transition metal of the periodic table, for example, a titanium atom, a zirconium atom or a hafnium atom, and Q is a halogen atom, a hydrocarbon group, or a neutral conjugated or unconjugated diene having 10 or less carbon atoms. is selected in the same or different combination from a neutral ligand capable of coordination with an anionic ligand and a lone pair, j is an integer of 1 to 4, R ^a and R ^B are the same or different from each other May be mononuclear or polynuclear hydrocarbon residues that can form a sandwich structure with M, Y is a carbon or silicon atom, ^RC and ^RD are the same or different from each other. It 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 to each other 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 the formula [A2], R ¹ is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R ^{2 to} R ¹⁰ are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group. They may be the same or different from each other, and the respective substituents 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 a neutral conjugate capable of coordinating with a halogen atom, a hydrocarbon group, a neutral conjugated or unconjugated diene having 10 or less carbon atoms, an anionic ligand, and a lone electron pair. Selected from the ligands in the same or different combinations, j is an integer of 1-4.

Among the crosslinked metallocene compounds represented by the general formula [A2], the crosslinked metallocene compound represented by the general formula [A3] is particularly preferable from the viewpoint of obtaining a polymer satisfying the above requirements in terms of polymerization characteristics, availability, and the above requirements.

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 the formula [A3], R ^1b is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R ^{2b to} R ^12b are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group. They may be the same or different, and the substituents 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 to 3, Q is a halogen atom, a hydrocarbon group, a neutral conjugated or unconjugated diene having 10 or less carbon atoms, an anionic ligand, and the like. Selected from neutral ligands that can be coordinated with lone electron pairs in the same or different combinations, j is an integer of 1-4.

<R ¹ to R ¹⁰ , R ^1b to R ^12b >
Examples of the hydrocarbon groups in R ¹ to R ¹⁰ and ^{R 1 b} to R ^{12 b} include linear hydrocarbon groups, branched hydrocarbon groups, cyclic saturated hydrocarbon groups, cyclic unsaturated hydrocarbon groups, and saturated hydrocarbon groups. Examples thereof include a group formed by substituting one or more hydrogen atoms possessed by the cyclic unsaturated hydrocarbon group 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 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 the alkyl group of the above with an aryl group.

Examples of the silicon-containing group in R ¹ to R ¹⁰ and ^{R 1 b} to R ^{12 b} include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group and the like-SiR ₃ (in the formula). , A plurality of Rs are independently alkyl groups or phenyl groups having 1 to 15 carbon atoms.)

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

Examples of the halogen atom in R ² to R ¹⁰ and ^{R 2 b} to R ^12b include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Of the substituents R ² to R ¹⁰ and R ^2b to R ^12b , two substituents (eg R ^2b and R ^3b , R ^3b and R ^4b , R ^5b and R ^6b , R ^6b and R ^7b , R ^8b and R ^9b , R ^9b and R ^10b , R ^10b and R ^11b , R ^11b and R ^12b ) may be bonded to each other to form a ring, and the ring formation is present at two or more positions in the molecule. You may.

In the present specification, examples of the ring (spiro ring, additional ring) formed by bonding two substituents to each other include an alicyclic ring and an aromatic ring. Specific examples 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 steric regularity, 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 a substituent which is a tertiary carbon. 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 preferable. Is a substituent in which the carbon having a free atomic value such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, a 1-adamantyl group is a tertiary carbon, and particularly preferably a tert-butyl group, 1- It is an adamantyl group.

In the general 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 hydrogen atoms or hydrocarbon groups, more preferably hydrocarbon groups, and even more preferably hydrocarbon groups 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 group is 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.}

Alternatively, when n = 1, ^{it is more preferable that R 9b} and R ^10b are bonded to 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.

<About M, Q, n and j>
M is a Group 4 transition metal, such as Ti, Zr or Hf, preferably Zr or Hf, and particularly preferably Zr.
Q indicates a halogen atom, a hydrocarbon group, a neutral conjugated or unconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand that can be coordinated with a lone electron pair.
Examples of the halogen atom in Q include fluorine, chlorine, bromine, and iodine.

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 methoxy and tert-butoxy; an aryloxy group such as phenoxy; a carboxylate group such as acetate and benzoate; and a sulfonate group such as mesylate and tosylate.

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 to 3, preferably 1 or 2, and more preferably 1. It is preferable that n is the above value from the viewpoint of efficiently obtaining the polymer to be produced.

j is an integer of 1 to 4, preferably 2.
In the above, preferred embodiments have been described with respect to the constitution of the crosslinked metallocene compound represented by the general formula [A2] or [A3], that is, R ^{1 to} R ¹⁰ , R ^{1b to} R ^12b , M, n, Q and j. In the present invention, any combination of the respective preferred embodiments is also a preferred embodiment. Such a crosslinked metallocene compound can be suitably used for obtaining the polymer of the present invention having the above physical characteristics.

Examples of the crosslinked metallocene compound represented by the general 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) -Il) -8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta [a] indene)) Zyroxide dichloride is particularly preferred. Here, the above-mentioned octamethylfluorene is 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b]. , h] Fluorene.

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

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 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.

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

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

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 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 the formula [B4], R ^c is a hydrocarbon group having 1 to 10 carbon atoms. The plurality of R ^ds are independently hydrogen atoms, halogen atoms, or hydrocarbon groups having 1 to 10 carbon atoms. In the production method using the above-mentioned olefin polymerization catalyst, a 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. Further, organoaluminum oxy compounds described in JP-A-2-167305, and aluminoxane having two or more kinds of alkyl groups described in JP-A-2-24701 and JP-A-3-103407 are also available. Can be preferably used.

The above-mentioned "benzene-insoluble or sparingly soluble" organic aluminum 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 atom. , Particularly preferably 2% by mass or less, refers to an organic aluminum oxy compound that is insoluble or sparingly soluble in benzene.
The above-exemplified organoaluminum oxy compound (b-1) may be used alone or in combination of two or more.

<< Ionic compound (b-2) >>
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 include 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 Patent 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, as the ionic compound (b-2), the compound represented by the general formula [B5] is preferable.

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 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-dialkylanilinium cations such as −dimethylanilinium cations, N, N-diethylanilinium cations, N, N, 2,4,6-pentamethylanilinium cations; 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 carbonium 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.

1. 1. When ^{Re +} is a carbocation cation (carbocation salt)
Examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-ditrifluoromethylphenyl) borate, and tris (4-methylphenyl) carbe. Examples thereof include niumtetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

2. When ^{Re +} is an ammonium cation (ammonium salt)
Examples of the ammonium salt 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 (trimethylammonium tetraphenylborate). o-tryl) 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. NS.

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

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

_{^{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, m is 0 <m ≦ 3, and n is. 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3.

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

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 aluminum, triaryl aluminum such as tri-tolyl aluminum, diisopropyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, Y and z are positive numbers, and z ≦ 2x.) Alkenyl aluminum such as isoprenyl aluminum; alkylaluminum alkoxides such as isobutylaluminum methoxydo and isobutylaluminum ethoxide; dimethylaluminum methoxyde, alkyl sesquichloride alkoxides such as ethylaluminum sesquichloride ethoxide, butyl aluminum sesqui butoxide; diethylaluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide general formula ^{_{R a 2.5 Al (oR b)}} 0.5 ( wherein, R ^a 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 , Ethylaluminum sesquibromid, etc. Alkylaluminum sesquihalide; ethylaluminum Partially halogenated alkylaluminum such as alkylaluminum dihalide such as dichloride; dialkylaluminum hydride such as diethylaluminum hydride and dibutylaluminum hydride, and 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.

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. Further, the organoaluminum compound (b-3) may be used alone or in combination of two or more.

<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.

《Inorganic compounds》
Inorganic compounds include porous oxides, inorganic halides, clay minerals, clays (usually composed mainly of the clay minerals), ion-exchange layered compounds (most clay minerals are ion-exchange layered). It is a 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. .. Composites or mixtures include 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 in the range of 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 in ^{the range of 100-700 m 2} / g; the pore volume is preferably in the range of ^{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 or a vibration mill. 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 in the form of 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 are exchangeable.

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 dense 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, a treatment for affecting the crystal structure of clay, and the like 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.

The guest compounds to be intercalated include 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.

《Organic compounds》
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 copolymer 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 characteristics of the olefin polymer, if necessary. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

<Construction of catalyst for olefin polymerization>
When the olefin is polymerized using the olefin polymerization catalyst, the amount of each component that can constitute the olefin polymerization catalyst is as follows. Further, in the catalyst for olefin polymerization, the content of each component can be set as follows.

(1) When polymerizing an olefin using a catalyst for olefin polymerization, the crosslinked metallocene compound (A) is usually 10 ^-9 to 10 ^-1 mol, preferably 10 ^-8 to 10 mol, per 1 liter of the reaction volume. It is used in an amount such that it is ^{-2 mol.}

(2) When the organoaluminum oxy compound (b-1) is used as a component of the catalyst for olefin polymerization, the compound (b-1) is a crosslinked metallocene compound with an 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 (A) is usually 0.01 to 5000, preferably 0.05 to 2000.

(3) When the ionic compound (b-2) is used as a component of the catalyst for olefin polymerization, the compound (b-2) is a total transition metal in the compound (b-2) and the crosslinked metallocene compound (A). It is used in an amount such that the molar ratio to the atom (M) [(b-2) / 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 a total transition metal in 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 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 catalyst for olefin polymerization, when the compound (B) is the organic aluminum 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; the compound (B) is ionic. When it is 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. Is an amount such that is 0.1 to 5; when the compound (B) is an organic aluminum 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.

[2] Polymerization Method In the production of the 4-methyl-1-pentene copolymer (B), the 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 the inert hydrocarbon medium 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. Aliphatic hydrocarbons; 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.

In the production method, the polymerization temperature of the olefin 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 the 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 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 production method may be synthesized by the above method and then subjected to post-treatment steps such as a known catalyst deactivation treatment step, catalyst residue removal step, and drying step, if necessary.

[Other ingredients]
The 4-methyl-1-pentene copolymer composition (X) is a 4-methyl-1-pentene (co) polymer (A) and 4 depending on its use, as long as the effects of the present invention are not impaired. At least one selected from other polymers different from the -methyl-1-pentene copolymer (B) and additives for resins can be optionally contained. Hereinafter, other polymers different from the 4-methyl-1-pentene (co) polymer (A) and the 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), a wide range of thermoplastic resins different from the 4-methyl-1-pentene (co) polymer (A) and the 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). It is more preferably less than or equal to%.

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-based resins: For example, low-density, medium-density, high-density polyethylene, polyethylene such as high-pressure low-density polyethylene, isotactic polypropylene, polypropylene such as syndiotactic polypropylene, poly1-butene, poly4-methyl- 1-Penten, Poly3-Methyl-1-pentene, Poly3-Methyl-1-butene, Ethylene / α-olefin copolymer, Polypropylene / 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 resin: For example, aliphatic polyamide (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612);
Thermoplastic polyester-based resin: For example, polyethylene terephthalate, polybutylene terephthalate, polyester-based elastomer;
Thermoplastic vinyl aromatic resin: For example, polystyrene, ABS resin, AS resin, styrene-based elastomer (styrene / butadiene / styrene block polymer, styrene / isoprene / styrene block polymer, styrene / isobutylene / styrene block polymer, hydrogenation of these Stuff);
Thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; vinyl acetate copolymer such as ethylene / vinyl acetate copolymer; ethylene / methacrylate acrylate copolymer; ionomer; ethylene / vinyl alcohol copolymer; polyvinyl Alcohol; Fluorine Resin; Polycarbonate; Polyacetal; Polyphenylene Oxide; Polyphenylene Sulfide Polygonide; Polyallylate; Polysulfone; Polyethersulfone; Rosin Resin; Terpen Resin and Petroleum Resin;
Copolymer rubber: For example, ethylene / α-olefin / diene copolymer, propylene / α-olefin / diene copolymer, 1-butene / α-olefin / diene copolymer, polybutadiene rubber, polyisobutylene rubber, neoprene. Rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, silicone rubber;
Etc. are exemplified. Among the above-mentioned thermoplastic polyolefin-based resins, for example, polyethylene and polypropylene can also be used as the crystal nucleating agent, and the preferable content in that case is 0.001 to 0.001 with respect to the total mass of the copolymer composition (X). It is 5% by mass.

Among the thermoplastic resins, preferably, low density, medium density, high density polyethylene, high pressure method 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-based elastomer, vinyl acetate copolymer, ethylene / methacryl Acid acrylate copolymers, ionomers, fluororesins, rosin resins, terpene resins and petroleum resins, more preferably polyethylene, isotactic polypropylene, in terms of heat resistance, low temperature resistance and flexibility. Syndiotactic polypropylene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer, vinyl acetate copolymer, styrene-based elastomer, rosin-based resin, terpene-based Resin and petroleum resin.

Part or all of the other polymer (D) may be a graft-modified polymer obtained by graft-modifying the polymer with a polar monomer. The graft modification is the same as the above << Graft modification >> shown for the 4-methyl-1-pentene (co) polymer (A).
The other polymer (D) may be used alone or in combination of two or more.

<< 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. , Antistatics, Weather Stabilizers, Heat Stabilizers, Antislip Agents, Foaming Agents, Crystallization Aids, Antifogging Agents, Antiaging Agents, Hydroxyl Absorbents, Impact Improvement Agents, Crosslinking Agents, Cocrosslinking Agents, Crosslinking Assistance Examples include agents, adhesives, softeners and processing aids.

The additive (C) may be used alone or in combination of two or more.
The content of the additive (C) is not particularly limited depending on the application as long as the object of the present invention is not impaired, but the additive to be blended with respect to the total mass of the copolymer composition (X). It is preferably 0.001 to 30% by mass for each.

As the nucleating agent, a known nucleating agent can be used in order to further improve the moldability of the copolymer composition (X), that is, to raise the crystallization temperature and increase the crystallization rate. Specifically, dibenzylidene sorbitol-based nucleating agent, phosphoric acid 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 salts thereof, 2,6-naphthalene acid dicarboxylic acid dicyclohexylamide, ethylene bisstearate amide and the like can be mentioned.

The amount of the nucleating agent to be blended is not particularly limited, but is that of the 4-methyl-1-pentene (co) polymer (A), the 4-methyl-1-pentene copolymer (B) and the 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.

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 an inorganic content (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and an organic pigment (azolake-based, thioindigo-based, phthalocyanine-based, anthraquinone-based). 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 copolymer composition (X).

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

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

Examples of the plasticizing agent include aromatic carboxylic acid ester (dibutyl phthalate, etc.), aliphatic carboxylic acid ester (methylacetylricinolate, etc.), aliphatic dialbon acid ester (adipic acid-propylene glycol-based polyester, etc.), and aliphatic. 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 to 4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4 to 30) (hardened castor oil, etc.), glycol esters of fatty acids, and fluidized fatty acids. Examples include paraffin.

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 tenside include amino acid type double-sided surfactants such as higher alkylaminopropionate, higher alkyldimethylbetaine, and betaine type amphoteric surfactants such as hydroxyethyl betaine at the time of higher alkyl.

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) hydrocinnamates] 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 based on 100 parts by mass of the total amount of the 4-methyl-1-pentene (co) polymer (A), the 4-methyl-1-pentene copolymer (B) and the other polymer (D). 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-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, and tri Peroxy cross-linking aids such as methylolpropane-N, N'-m-phenylenedi maleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylpropantrimethacrylate, Polyfunctional methacrylate monomers such as allyl 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. In particular, in the present invention, divinylbenzene is preferably used. Divinylbenzene is easy to handle, has good compatibility with polymers, has an action of solubilizing organic peroxides, and acts as a dispersant for organic peroxides. 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 above-mentioned cross-linking aid is based on 100 parts by mass of the total amount of 4-methyl-1-pentene (co) polymer (A), 4-methyl-1-pentene copolymer (B) and other polymers (D). It is preferably used in a proportion of 0.05 to 10 parts by mass.

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, and atactic polypropylene, and ester-based plastics such as dioctyl phthalate, dioctyl adipate, and dioctyl sebacate. Agents, carbonate ester-based plasticizers such as diisododecyl carbonate, other microcrystallin wax, sub (factis), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, hydrocarbon-based synthetic lubricating oil, and the like. Of these, petroleum-based softeners and hydrocarbon-based synthetic lubricating oils are preferable.

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

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

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 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 4-methyl-1-pentene (co) polymer (A) and 4-methyl-1-pentene copolymer (B) may occur. be. The kneading time is usually 0.1 to 30 minutes, particularly preferably 0.5 to 5 minutes. If the kneading time is less than 0.1 minutes, melt kneading is not sufficiently performed, and if the kneading time exceeds 30 minutes, 4-methyl-1-pentene (co) polymer (A) and 4-methyl-1 are used. -Pyrolysis of components such as the penten copolymer (B) may occur.

<Molded body>
A molded product is obtained by molding the 4-methyl-1-pentene copolymer composition (X).
(1) Molding Method As the molding method of the 4-methyl-1-pentene copolymer composition (X), various known molding methods can be applied, for example, injection molding, extrusion molding, injection stretching blow molding method, blow. Various molding methods such as molding method, cast molding method, calender molding method, press molding, stamping molding, inflation molding, roll molding and the like 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, a non-woven fabric shape, and the like.

(2) Applications The molded product of the present invention can be used without restriction in applications where a conventional 4-methyl-1-pentene polymer can be used, but impact resistance, heat resistance and transparency are required. It is more suitable for applications. More specific applications include medical instruments, medical packaging materials, laboratory equipment, cosmetic containers, baby products, food containers, microwave oven steam sterilization containers and equipment.

There are no restrictions on the use of the film, for example, packaging materials for foods, 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. Other uses include, for example, the following. Examples of applications of the molded product according to the present invention are listed below, but the application is not particularly limited thereto.

Examples of containers include tableware, tampering containers, kitchen utensils, retort containers, frozen storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, chilled confectionery cups, cups, baby bottles, beverage bottles and other food containers. Retort container, bottle container, etc., blood transfusion set, medical bottle, medical container, medical hollow bottle, medical bag, infusion bag, blood storage bag, infusion bottle, chemical container, detergent container, softener container, bleaching agent Containers, shampoo containers, rinse containers, cosmetic containers, perfume containers, toner containers, powder containers, adhesive containers, gasoline tank containers, kerosene containers, food containers, heat-resistant containers, medical containers, animal cages, Examples include physics and chemistry laboratory equipment.

Examples of packaging materials include food packaging materials, 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, and freshness. Retention film, 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 use Examples include plastic wrap and baking cartons.

Examples of the film include 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 curing film for a carbon fiber composite material. Release film, 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 film for semiconductor encapsulation, 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 film for various rubber sheets, Release film for urethane curing, release film such as epoxy curing release film, solar cell sealing sheet, solar cell back sheet, plastic film for solar cell, battery separator, separator for lithium ion battery, for fuel cell Electrolyte film, adhesive / adhesive separator, light guide plate, optical disk, dicing tape / back grind tape / die bonding film, double-layer FCCL, film Condenser film, etc. , 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 product protective film, mobile phone Protective film, personal computer protective film, touch panel protective film, window glass protective film, baking finish film, masking film, condenser film, capacitor film, tab lead film, fuel cell capacitor film, reflective film, diffusion film, laminated Body (including glass), radiation-resistant film, γ-ray resistant film, protective film such as porous film, heat-dissipating film / sheet, mold for manufacturing electronic component encapsulants, LED molds, laminates for high-frequency circuits, high-frequency cables 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, for curing glass fiber composite material Release paper, 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 Examples thereof include films, synthetic papers, display films, display conductive films, and display barrier films.

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-voltage wire porcelain, wiring duct, cosmetic / perfume spray tube, medical tube, infusion tube, Pifus, 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, airbag 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 Automobiles such as wheels, wire harness covers, seat adjuster covers, etc. Interior / exterior materials, 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, glomets, 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, panoramic roof , Solenoy valve, ECU case, unit connection connector, alternator, HEV terminal block, electromagnetic valve, coil encapsulation parts, skin material for furniture, footwear, clothing, bags, building materials, etc., building sealant, waterproof sheet, building material sheet , 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), Port supplies (eg sports grips, protectors), sports armor, rackets, mouth guards, balls, golf balls, carrying tools (eg carrying shock absorbing glyphs, shock absorbing sheets), 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 and 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 spouts, etc. Outlet, 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 bowl, Escalator parts, ultrasonic motor housings, absolute encoders, small pump housings, TV parts, hair dryer housings, lighting covers, miscellaneous goods, coffee drippers, humidifier parts, irons Parts, water supply parts, water cylinders, combs, pencil cases, pencil cases, pencil sharpeners, sports and leisure goods, ski goggles, karate / kendo armor, surfing fins, musical instruments, fish tanks, sandals, snow scrapers, fishing rod cases, toys, shoe soles. , Sole sole, midsole / inner sole of shoes, sole, sandals, chair skin, bag, school cell, jumper coat and other clothing, band, stick, ribbon, notebook cover, book cover, key holder, pencil case, wallet, Chopsticks, rangers, microwave cooking pans, business card holders, regular holders, suckers, toothbrushes, flooring materials, gym mats, power tool parts, farm equipment parts, heat dissipation materials, transparent substrates, soundproofing materials, sound absorbing materials, cushioning materials, electric wire cables , Shape memory materials, connectors, switches, plugs, home appliances parts (motor parts, housings, etc.), medical gaskets, speaker diaphragms, medical caps, chemical plugs, gaskets, baby foods, dairy products, pharmaceuticals, sterile water, etc. Packing materials for high temperature treatment such as boiling treatment and high pressure steam sterilization after filling in bottles, industrial sealing materials, industrial sewing tables, number plate housings, cap liners such as PET bottle cap liners, protective film adhesive layer, hot Adhesive materials such as melt adhesive, stationery, office supplies, OA printer legs, FAX legs, sewing machine legs, motor support mats, audio vibration isolation materials and other precision equipment / OA equipment support members, heat-resistant packing for OA, animal cages, beakers , Physical and chemical 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 sheets, As a desk mat, as a fiber, for example, monofilament, multifilament, cut fiber, hollow thread, non-woven fabric, elastic non-woven fabric, fiber, waterproof cloth, breathable textile or cloth, paper diaper, sanitary goods, sanitary goods, filter, Bug filter, dust filter, air cleaner, hollow thread filter, water purification filter, cloth, paper, gas separation membrane, artificial liver (case, hollow thread), filter back-penetration membrane, artificial cardiopulmonary, syringe syringe, three-way Live stopper, infusion set, surgeon's instrument, flow meter, dental instrument, contact lens sterilization instrument, inhalation mask, analytical cell, milking machine, fire alarm, fire extinguisher, helmet, protective glasses, IC carrier, pickup lens, Burn-in socket, etc. ..

In addition, coating materials, films obtained by coating, sheets, mold release materials, water-shooting materials, insulating films, adhesives, adhesives, coated papers, transparent sealants, sealants, hot melt type adhesives, solvent type adhesives It is also suitably used for agents, film-like adhesives, cloth tapes, kraft tapes, elastic adhesives and the like.

Further, the 4-methyl-1-pentene copolymer composition (X) can also be processed into a fine powder by a pulverization treatment. The obtained fine powder can be used as, for example, an additive for an ink composition or a paint composition, an additive for a powder composition for metallurgy, an additive for a powder composition for ceramic sintering, an additive for a pressure-sensitive adhesive, and a rubber. It can be used as an additive, a mold release agent for toner, 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.

The present invention will be described in detail based on examples, but the present invention is not limited to these examples.
[Synthesis of transition metal complex]
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 was synthesized. This compound is also referred to as "metallocene compound (a)".

[Production Example 1] 4-Methyl-1-pentene / 1-hexadecene / 1-octadecene copolymer (B1)
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 therein, 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.

In a SUS autoclave with an internal volume of 1,500 ml that has been sufficiently dried and replaced with nitrogen, 500 mL of 4-methyl-1-pentene and 250 mL of cyclohexane, 94 mL of linearene 168 (manufactured by Idemitsu Kosan) (1-hexadecene, 1-octadecene mixture) and tri 0.5 mmol of a hexane solution of isobutylaluminum (Al concentration: 0.5 M) was charged, 124.3 mL of hydrogen was added, and then the polymerization temperature was raised to 60 ° C. with stirring at 850 rpm.

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, methanol was added to terminate the polymerization.

The polymer solution taken out from the cooled / depressurized autoclave was put into a 1: 1 solution of acetone and methanol to precipitate the polymer, and the polymer was collected by filtration. Then, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 107.7 g of 4-methyl-1-pentene / linearene 168 copolymer (B1).

[Production Example 2] 4-Methyl-1-pentene / 1-hexene copolymer (B2)
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 therein, 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.

A hexane solution of 4-methyl-1-pentene 350 mL, cyclohexane 250 mL, 1-hexene 250 mL and triisobutylaluminum (Al concentration: 0.5 M) 0 in a sufficiently dried and nitrogen-substituted SUS autoclave with an internal volume of 1,500 ml. After charging 5.5 mmol and adding 71.0 mL of hydrogen, the polymerization temperature was raised to 60 ° C. with stirring at 850 rpm.

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

The polymer solution taken out from the cooled / depressurized autoclave was put into a 1: 1 solution of acetone and methanol to precipitate the polymer, and the polymer was collected by filtration. Then, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 55.8 g of 4-methyl-1-pentene / 1-hexene copolymer (B2).

[Production Example 3] 4-Methyl-1-pentene / ethylene copolymer (B'1)
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 therein, 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.

A SUS autoclave having an internal volume of 1,500 ml, which was sufficiently dried and replaced with nitrogen, was charged with 750 mL of 4-methyl-1-pentene and 0.5 mmol of a hexane solution of triisobutylaluminum (Al concentration: 0.5 M), and hydrogen was added. After adding 35.5 mL, the polymerization temperature was raised to 70 ° C. with stirring at 850 rpm. After adding nitrogen at that temperature until the internal pressure of the autoclave reached 0.34 MPaG, the pressure was increased with ethylene until the total pressure reached 0.6 MPaG.

0.3 mL of the above catalyst solution (concentration of metallocene compound (a): 0.3 μmol) was charged into this autoclave to start polymerization, and ethylene was supplied so as to maintain a total pressure of 0.6 MPaG until the polymerization was stopped. After 9 minutes, methanol was added to terminate the polymerization.

The polymer solution taken out from the cooled / depressurized autoclave was put into a 1: 1 solution of acetone and methanol to precipitate the polymer, and the polymer was collected by filtration. Then, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 94.4 g of 4-methyl-1-pentene / ethylene copolymer (B'1).

[Production Example 4] 4-Methyl-1-pentene / ethylene copolymer (B'2)
A SUS autoclave having an internal volume of 4 L, which was sufficiently dried and replaced with nitrogen, was charged with 1.95 mmol of 4-methyl-1-pentene (1950 mL) and a hexane solution of triisobutylaluminum (Al concentration: 0.5 M) in terms of Al. After adding 91 mL of hydrogen, the polymerization temperature was raised to 70 ° C. with stirring at 450 rpm. After adding nitrogen at that temperature until the internal pressure of the autoclave reached 0.25 MPaG, the pressure was increased with ethylene until the total pressure reached 0.6 MPaG.

0.5 mL of the above catalyst solution (concentration of metallocene compound (a): 0.5 μmol) was charged into the autoclave to start polymerization, and after 20 minutes, methanol was added to terminate the polymerization. The polymer solution taken out from the cooled / depressurized autoclave was put into methanol to precipitate the polymer, and the polymer was collected by filtration.
Then, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 81.1 g of 4-methyl-1-pentene / ethylene copolymer (B'2).

[Production Example 5] 4-Methyl-1-pentene / propylene copolymer (B'3)
A SUS autoclave having an internal volume of 1,500 ml, which was sufficiently dried and replaced with nitrogen, was charged with 750 mL of 4-methyl-1-pentene and 0.5 mmol of a toluene solution of triisobutylaluminum (Al concentration: 0.5M), and hydrogen was added. After adding 35.5 mL, the polymerization temperature was raised to 60 ° C. with stirring at 850 rpm.

0.3 mL of the catalyst solution (concentration of metallocene compound (a): 0.3 μmol) was charged into the autoclave to start polymerization, and then the temperature of the autoclave was adjusted to 30 ° C. for 60 minutes. 60 minutes after the start of the polymerization, 3 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure.

Acetone was poured into the reaction solution with stirring. The obtained rubber-like polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours to obtain 45.3 g of 4-methyl-1-pentene / ethylene copolymer (B'3).

[Production Example 6] 4-Methyl-1-pentene / 1-butene copolymer (B'4)
In a sufficiently dried and nitrogen-substituted SUS autoclave having an internal volume of 4 L, 740 mL of 4-methyl-1-pentene, 1210 mL of cyclohexane and a hexane solution of triisobutylaluminum (Al concentration: 0.5 M) were added to 1.95 mmol in terms of Al. After charging and adding 61 mL of hydrogen, 400 g of 1-butene was added while stirring at 450 rpm, and then the polymerization temperature was raised to 60 ° C.

3.0 mL of the above catalyst solution (concentration of metallocene compound (a): 3.0 μmol) was charged into the autoclave to start polymerization, and after 21 minutes, methanol was added to terminate the polymerization.
The polymer solution taken out from the cooled / depressurized autoclave was put into methanol to precipitate the polymer, and the polymer was collected by filtration. Then, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 178.0 g of 4-methyl-1-pentene / 1-butene copolymer (B'4).

[Production Example 7] 4-Methyl-1-pentene / 1-hexene copolymer (B'5)
Polymerization was carried out according to Example 5 of JP-A-2008-144155 to obtain 50.2 g of 4-methyl-1-pentene / 1-hexene copolymer (B'5).

[Production Example 8] 4-Methyl-1-pentene / 1-decene copolymer (A1)
In Comparative Example 7 of International Publication No. 2006/054613, the 4-methyl-1-pentene / 1-decene copolymer (A1) was obtained by changing the ratio of 4-methyl-1-pentene to 1-decene. (Hereinafter, also referred to as a polymer (A1)) was obtained.

[Production Example 9] 4-Methyl-1-pentene / 1-decene copolymer (A2)
[Preparation of solid catalyst components]
In a three-necked flask equipped with a 100 mL stirrer fully substituted with nitrogen at 30 ° C., 32 mL of purified decan and solid polymethylaluminoxane (manufactured by Tosoh Finechem) were charged at 14.65 mmol in terms of aluminum atoms under a nitrogen stream. It was added and made into a suspension. To the suspension, 50 mg (0.059 mmol in terms of zirconium atom) of the previously synthesized catalyst (A) was prepared as a 4.6 mmol / L toluene solution, and 12.75 mL of this solution was added with stirring. After 1.5 hours, the stirring was stopped, and the obtained catalyst component was washed 3 times with 50 mL of decan by the decantation method and suspended in the decan to obtain 50 mL of the slurry liquid (B). The Zr loading ratio was 100% in this catalyst component.

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

[Polymerization reaction]
425 mL of purified decane and 0.5 mL (1 mol) of diisobutylaluminum hydride decane solution (2.0 mmol / mL in terms of aluminum atoms) were added to a SUS polymerizer equipped with a stirrer with an internal volume of 1 L at room temperature and under a nitrogen stream. I charged it. Next, 0.0005 mmol of the previously prepared decan slurry (C) as a prepolymerization catalyst component was added in terms of zirconium atoms, and 50 NmL of hydrogen was charged (first hydrogen charge). Then, a mixed solution of 250 mL of 4-methyl-1-pentene and 3.3 mL of 1-decene was continuously charged into the polymerizer at a constant rate over 2 hours. The time at which the charge was started was defined as the start of polymerization, the temperature was raised to 45 ° C. over 30 minutes from the start of polymerization, and then the temperature was maintained at 45 ° C. for 4 hours. 150 minutes after the start of polymerization, 90 NmL of hydrogen was charged (second hydrogen charge). After 4.5 hours from the start of the polymerization, the temperature was lowered to room temperature, the pressure was depressurized, and then the polymerization solution containing the white solid was immediately filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80 ° C. for 8 hours to obtain a 4-methyl-1-pentene / 1-decene copolymer (A2).

[Production Example 10] 4-Methyl-1-pentene / 1-decene copolymer (A3)
Polymerization was carried out as in Production Example 9 except that the amount of 1-decene charged was 3.2 mL to obtain a 4-methyl-1-pentene / 1-decene copolymer (A3).

[Examples 1 to 6, Comparative Examples 1 to 10]
For Examples 1 to 6 and Comparative Examples 2 to 10, various polymers were mixed at a ratio according to Table 2 to obtain a composition by the following method, and subsequently, a press sheet was prepared. The composition prepared in Examples 1 to 6 is the 4-methyl-1-pentene copolymer composition (X) of the present invention.
For Comparative Example 1, the polymer A1 was used alone and melt-kneaded by the following method to prepare a press sheet.

In Comparative Example 9, as another polymer D1, Tough Tech (trademark) H1221 manufactured by Asahi Kasei Corporation was mixed and used at a ratio according to Table 2, and a press sheet was prepared by the following method.
In Comparative Example 10, as another polymer D2, Kraton (trademark) G1645M manufactured by Kraton was mixed and used at a ratio according to Table 2, and a press sheet was prepared by the following method.

[Melting kneading and preparation of press sheet]
0.2 parts by mass of BASF's Irgafoss ™ as a secondary antioxidant and BASF's Irga as a heat-resistant stabilizer with respect to 100 parts by mass of each polymer or mixture thereof obtained in Production Examples 1 to 10. 0.2 parts by mass of Knox ™ 1010 was blended. Next, using a lab plast mill (2-axis batch type melt-kneading device) manufactured by Toyo Seiki Co., Ltd., melt-kneading was performed at a set temperature of 260 ° C. under the conditions of a charge amount of 40 g (device batch volume: 60 cm ³ ), 50 rpm, and 5 minutes. , The composition was prepared.

The obtained composition was set to 260 ° C. using a hydraulic heat press machine manufactured by Shinto Metal Industry Co., Ltd., and the residual heat was set to about 3 to 7 minutes, pressurized at 10 MPa for 3 to 5 minutes, and then set to 20 ° C. A press sheet having a thickness of 0.5 mm, a thickness of 1 mm, a thickness of 2 mm, or a thickness of 3 mm was prepared by compressing (cooling) at 10 MPa for about 5 minutes using a hydraulic heat press machine manufactured by Shinto Metal Industry Co., Ltd. A brass plate having a thickness of 5 mm was used as the hot plate. The press sheet prepared by the above method was used for tensile elastic modulus test, Izod impact test, Vicat softening temperature measurement, and HAZE measurement.

[Measurement conditions for various physical properties]
Various physical properties of the polymers obtained in Production Examples 1 to 10 and the press sheets obtained in Examples 1 to 6 and Comparative Examples 1 to 10 were measured by the following methods. The measurement results of each polymer are shown in Table 1, and the measurement results of each press sheet are shown in Table 2. Regarding the comonomer composition, ultimate viscosity [η], and molecular weight distribution (Mw / Mn) of each polymer, each polymer before melt-kneading was used as it was for measurement. For the DSC measurement and the solid viscoelasticity measurement, the press sheet after melt-kneading was used for the measurement. In the table, "-" indicates that the measurement is not performed. FIG. 1 shows the relationship between the tensile elastic modulus and the IZOD impact strength of the compositions obtained in Examples and Comparative Examples.

[Measurement of comonomer composition]
The content of the structural units derived from the comonomer 4-methyl-1-pentene, ethylene and α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) can be determined by the following equipment and conditions. ¹³ Calculated from C-NMR spectrum.

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

Content of constituent units derived from comonomer (%) = [P / (P + M)] × 100
Here, P indicates the total peak area of the comonomer backbone methine signal, and M indicates the total peak area of the 4-methyl-1-pentene backbone methine signal.

[Measurement of extreme viscosity [η]]
The ultimate viscosity [η] was measured at 135 ° C. using a decalin solvent. Specifically, about 20 mg of the sample 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 of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity (see the formula below).
[Η] = lim (ηsp / C) (C → 0)

[Measurement of molecular weight distribution (Mw / Mn)]
The molecular weight distribution was measured by GPC.
Equipment: Gel permeation chromatograph HLC-8321 GPC / HT type (manufactured by Tosoh Corporation)
Organic solvent: o-dichlorobenzene Column: 2 TSKgel GMH6-HT, 2 TSKgel GMH6-HTL columns (both manufactured by Tosoh Corporation)
Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution v
Temperature: 140 ° C
Molecular weight conversion: PS conversion / general-purpose calibration method

The coefficient of the Mark-Houwink viscosity formula was used for the calculation of the general-purpose calibration. For the Mark-Houwink coefficient of PS, the values described in the literature (J. Polymer. Sci., Part A-2, 8, 1803 (1970)) were used.
Mw / Mn was calculated by analysis using a calibration curve using a standard polystyrene sample by a known method.

[Measurement of 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 press sheet, 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 ° C. The temperature is lowered to 20 ° C. at a cooling rate of / 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 to 50. The temperature was lowered to ℃. The melting peak developed at the time of the second temperature rise was defined as the melting point (Tm).

[Dynamic Viscoelasticity Measurement]
Using a 2 mm thick press sheet, a strip piece of 30 mm × 10 mm × 2 mm necessary for dynamic viscoelasticity measurement was further cut out. Using MCR301 manufactured by ANTONPaar, the temperature dependence of dynamic viscoelasticity in the range of -30 to 240 ° C. was measured at a frequency of 10 rad / s, and the temperature at which the loss tangent (tan δ) was the maximum value and the maximum value of tan δ. Was measured.
Normally, the temperature at which the maximum value of tan δ is obtained is the temperature at which the glass transition occurs.

[Tensile test (YM)]
Using a 2 mm thick press sheet, a No. 2 1/2 size dumbbell type test piece was prepared in accordance with JIS K7113, and measured with a universal tensile tester 3380 manufactured by Instron at a tensile speed of 30 mm / min. A tensile test was carried out under the condition of a temperature of 23 ° C., and the tensile elastic modulus (YM) was measured.

[Izod impact test]
Using a 3 mm thick press sheet, an Izod impact test was carried out at 23 ° C. with a digital impact tester DG-IB type manufactured by Toyo Seiki Seisakusho Co., Ltd. in accordance with ASTM D256, and the Izod impact strength was measured.

[Vicat softening temperature test]
Using a 3 mm thick press sheet, in accordance with ASTM D1525, using a testing machine manufactured by Yasuda Seiki Co., Ltd., perform a Vicat softening temperature test in silicone oil at a heating rate of 50 ° C. per hour and a test load of 10 N. It was carried out and the Vicat softening temperature was measured.

[Internal haze measurement]
The haze (HAZE) measurement was performed using a 1 mm thick press sheet and a haze / transmittance meter HM-150 manufactured by Murakami Color Research Institute Co., Ltd.

[Comparison between Examples and Comparative Examples]
From Table 2 and FIG. 1, it can be seen that the impact strength of the examples is significantly superior to that of the comparative examples. Further, in the composition of the comparative example, the IZOD impact strength was not improved even if the content of the copolymer was increased and the tensile elastic modulus was decreased, but in the example, the composition having a low tensile elastic modulus was not observed. It can be seen that a higher IZOD impact strength was obtained. Further, it can be seen that the examples are in a preferable range in terms of the bicut softening point, which is an index of heat resistance, and the internal haze, which is an index of transparency.

Claims (3)

50.0 to 95.0 parts by mass of 4-methyl-1-pentene (co) polymer (A) satisfying the following requirements (A-a) to (A-c) and the following requirements (B-a) to (A-c). Contains 5.0 to 50.0 parts by mass of the 4-methyl-1-pentene copolymer (B) satisfying B-e) (provided that the total of (A) and (B) is 100 parts by mass). , 4-Methyl-1-pentene copolymer composition (X).
(A-a) The content (U1) of the structural unit derived from 4-methyl-1-pentene is 100 to 90.0 mol%, and ethylene and α-olefin (4-methyl) having 3 to 20 carbon atoms. The content (U2) of the structural unit derived from the olefin selected from the group consisting of -1-pentene) is 0 to 10.0 mol%.
(A-b) The ultimate viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.0 dl / g.
(Ac) The melting point (Tm) measured by DSC is in the range of 200 to 260 ° C.
(BA) The content (U3) of the structural unit derived from 4-methyl-1-pentene is 20.0 to 95.0 mol%, and ethylene and α-olefin (4) having 3 to 20 carbon atoms. The content (U4) of the structural unit derived from −methyl-1-pentene) is 5.0 to 80.0 mol%.
(Bb) The ultimate viscosity [η] measured in 135 ° C. decalin is 0.5 to 5.0 dl / g.
(B-c) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is 1.0 to 3.5. be.
(Bd) The melting point (Tm) measured by DSC is in the range of less than 200 ° C., or the peak indicating the melting point does not appear in the DSC measurement.
(B-e) In the dynamic viscoelasticity measurement in the temperature range of -30 to 240 ° C. at a frequency of 10 rad / s, the temperature (Tg) at which tan δ is the maximum value in the temperature range of -30 ° C. to 50 ° C. is 10. It is below 0.0 ° C. The 4-methyl-1-pentene copolymer composition (X) according to claim 1, which satisfies the following requirements (X-1) to (X-3).
(X-1) The tensile elastic modulus measured according to JIS K7113 is 400 MPa or more.
(X-2) The Izod impact strength at 23 ° C. measured according to ASTM D256 is 50 J / m or more.
(X-3) The Vicat softening temperature measured according to ASTM D1525 is 100 ° C. or higher. A molded product containing the 4-methyl-1-pentene copolymer composition (X) according to claim 1 or 2.

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