JP6439031B2 - 4-methyl-1-pentene copolymer composition - Google Patents

Description

  The present invention relates to a composition containing 4-methyl-1-pentene copolymer, a molded article comprising the composition, and uses thereof. More specifically, a composition containing 4-methyl-1-pentene copolymer having excellent balance of stress absorption, heat resistance, low temperature, and transparency, a molded article comprising the composition, and uses thereof About.

  Conventionally, a polymer having a large peak value of a loss coefficient tan δ of dynamic viscoelasticity measurement, which is a vibration damping index, has been used as a damping material having vibration characteristics. Examples of a polymer suitable as a vibration damping material include styrene-isoprene-styrene block copolymer (SIS) or a hydrogenated product thereof. Since SIS has a peak of a large tangent loss tan δ near room temperature, it has excellent vibration damping characteristics near room temperature. However, since tan δ peak is sharp, it has poor vibration damping performance except near the peak temperature. Further, since the hydrogenation SIS is manufactured by a process consisting of two stages of polymerization and hydrogenation, the production cost is high and the industrial application range is limited.

  On the other hand, polyolefins such as polypropylene and 4-methyl-1-pentene homopolymer have a tan δ peak near room temperature, but the peak value is small. Polyvinyl chloride (PVC) vibration damping materials generate toxic gases during incineration. May adversely affect the environment.

  In addition, 4-methyl-1-pentene / α-olefin copolymer is a resin excellent in heat resistance as well as light weight, transparency, gas permeability, chemical resistance, food, medical, electronic information, home appliances, laboratory equipment. It is used in various fields such as stationery. For example, Patent Document 1 discloses 4-methyl-1-pentene copolymers, which describe that these are excellent in heat resistance and various mechanical properties. Patent Document 2 describes a 4-methyl-1-pentene / α-olefin copolymer, a composition containing the copolymer, applications for these damping materials, and shock absorption.

  However, the composition of the 4-methyl-1-pentene copolymer and the softening agent disclosed in Patent Document 2 is inferior in heat resistance and is transparent in the composition with a thermoplastic resin in order to satisfy heat resistance. The composition with 4-methyl-1-pentene polymer in order to satisfy the transparency, the low temperature property and the stress absorption property are inferior, and the stress absorption property, heat resistance, There is a further problem because it has not been possible to provide a material that is excellent in both low temperature and transparency.

International Publication No. 2005/121192 Pamphlet International Publication No. 2011/055803 Pamphlet

  An object of the present invention is to obtain a 4-methyl-1-pentene polymer composition having an excellent balance of stress absorption, heat resistance, low temperature, and transparency.

The present invention provides 10 to 100 parts by mass of 4-methyl-1-pentene polymer (A) satisfying the following requirements (a) to (c), and 4-methyl satisfying the following requirements (o) to (q). -1-pentene copolymer (B) is 90 to 0 parts by mass (provided that the total of component (A) and component (B) is 100 parts by mass), and component (A) and component (B) The 4-methyl-1-pentene polymer composition comprises 5 to 150 parts by mass of the softening agent (C) with respect to 100 parts by mass in total.
(A) The structural unit derived from 4-methyl-1-pentene is in the range of 80 to 91 mol%, and the structural unit derived from at least one of α-olefins having 2 to 20 carbon atoms is in the range of 9 to 20 mol%. [However, the total amount of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from α-olefin is defined as 100 mol%. ].
(B) The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is in the range of 0.5 to 5.0 dl / g.
(C) The melting point (Tm) measured by DSC is in the range of 110 ° C to 160 ° C.
(O) The structural unit derived from 4-methyl-1-pentene is derived from at least one of α-olefins (excluding 4-methyl-1-pentene) having 79 to 60 mol% and 2 to 4 carbon atoms. The structural unit is in the range of 40 to 21 mol% [however, the total amount of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from the α-olefin is 100 mol%. ].
(P) The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is in the range of 0.5 to 5.0 dl / g.
(Q) The melting point (Tm) measured by DSC is less than 110 ° C. or no melting point is observed.

  The 4-methyl-1-pentene polymer composition of the present invention maintained high transparency and stress absorption, which was difficult with the conventionally proposed 4-methyl-1-pentene polymer composition. As such, it is possible to provide a molded article and a film / sheet having heat resistance and low temperature, and excellent transparency and stress absorption.

<4-Methyl-1-pentene polymer (A)>
The 4-methyl-1-pentene polymer (A) constituting the 4-methyl-1-pentene polymer composition of the present invention is characterized by satisfying the following requirements (a) to (c).

[Requirement (a)]
(A) 80 to 100 mol% of structural units derived from 4-methyl-1-pentene, and 0 to 20 mol% of structural units derived from at least one kind of α-olefin having 2 to 20 carbon atoms. It is a homopolymer of a certain 4-methyl-1-pentene, and a copolymer of 4-methyl-1-pentene and an α-olefin. In addition, when the α-olefin is copolymerized, the total amount of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from the α-olefin is 100 mol%.

  Specific examples of the α-olefin having 2 to 20 carbon atoms copolymerized with 4-methyl-1-pentene include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl- Suitable examples include 1-butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicocene and the like. It is done.

  Among these, from the viewpoint of the copolymerizability and the physical properties of the obtained copolymer, ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-hexadecene, 1-heptadecene, 1-octadecene, and more preferably ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene 1-heptadecene and 1-octadecene, more preferably ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1-heptadecene and 1-octadecene.

These α-olefins having 2 to 20 carbon atoms can be used alone or in combination of two or more.
The 4-methyl-1-pentene polymer (A) may contain structural units derived from other polymerizable compounds in addition to the α-olefin as long as the object of the present invention is not impaired.

  Examples of such other polymerizable compounds include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or the like Derivatives; Conjugated dienes such as butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5- Heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- Isopropylidene-2-norbol , 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc. Non-conjugated polyenes.

  When each structural unit is in the above range, the 4-methyl-1-pentene polymer composition containing the 4-methyl-1-pentene polymer (A) is excellent in moldability and is obtained from the composition. The body is excellent in stress absorption and transparency.

[Requirement (b)]
(B) Intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent 0.5 to 5.0 dl / g, preferably 1.0 to 4.0 dl / g, more preferably 1.2 to 3.5 dl / g It is in the range of g.

  The 4-methyl-1-pentene polymer composition containing the 4-methyl-1-pentene polymer (A) having an intrinsic viscosity [η] in the above range has good fluidity and is molded. In particular, the molded product obtained from the composition is excellent in transparency, heat resistance, and stress absorbability.

[Requirement (c)]
(C) The melting point ( _Tm ) measured by DSC is in the range of 110 ° C to 240 ° C.
The melting point (Tm) is a value that varies depending on the stereoregularity of the polymer and the amount of α-olefin copolymerized, and can be controlled and adjusted to a desired composition using an olefin polymerization catalyst described later. Is possible.

The 4-methyl-1-pentene polymer composition containing the 4-methyl-1-pentene polymer (A) having a melting point (T _m ) value within the above range is excellent in heat resistance, and from the composition. The obtained molded body is superior in transparency, heat resistance and stress absorption.

  When the 4-methyl-1-pentene polymer (A) according to the present invention is used for the 4-methyl-1-pentene polymer composition of the present invention, it is not limited to one type as long as the above range is satisfied. More than one species may be used.

  The 4-methyl-1-pentene polymer (A) according to the present invention preferably has relatively few structural units derived from 4-methyl-1-pentene in the above range and a relatively low melting point in the above range. The number of structural units derived from the melting point of 4-methyl-1-pentene polymer (A1) and 4-methyl-1-pentene is relatively large in the above range, and the melting point is relatively high in the above range. It can be divided into 1-pentene polymer (A2).

<< 4-methyl-1-pentene polymer (A1) >>
The 4-methyl-1-pentene polymer (A1) according to the present invention has (a1) a structural unit derived from 4-methyl-1-pentene of 80 mol% or more and less than 91 mol%, and has 2 to 20 carbon atoms. The structural unit derived from at least one of the α-olefins is 9 mol% or more and 20 mol% or less (provided that the total amount of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from the α-olefin is 100 mol%).

  In the 4-methyl-1-pentene polymer (A1) according to the present invention, the upper limit of the structural unit derived from 4-methyl-1-pentene is preferably 90 mol%, more preferably 87 mol%, and the lower limit. Is preferably 81 mol%, more preferably 83 mol%. The upper limit of the structural unit derived from at least one kind of α-olefin is preferably 19 mol%, more preferably 17 mol%, and the lower limit is preferably 10 mol%, more preferably 13 mol%.

The 4-methyl-1-pentene polymer (A1) according to the present invention has (c1) a melting point (T _m ) measured by DSC of 110 to 160 ° C., preferably 115 to 160 ° C., more preferably 120. It is -160 degreeC, More preferably, it exists in the range of 125-160 degreeC.

  Since 4-methyl-1-pentene polymer (A1) has an excellent balance between heat resistance and stress absorption, the resulting 4-methyl-1-pentene polymer composition is also resistant to heat and stress. Excellent balance of sex.

<< 4-methyl-1-pentene polymer (A2) >>
The 4-methyl-1-pentene polymer (A2) according to the present invention has (a2) 91 to 100 mol% of structural units derived from 4-methyl-1-pentene and α-carbon having 2 to 20 carbon atoms. The structural unit derived from at least one kind of olefin is in the range of 9 to 0 mol% (provided that the total amount of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from α-olefin is 100 mol%. ).

  In the 4-methyl-1-pentene polymer (A2) according to the present invention, the upper limit of the structural unit derived from 4-methyl-1-pentene is preferably 99 mol%, more preferably 98 mol%, and the lower limit. Is preferably 91.5 mol%, more preferably 92 mol%. The upper limit of the structural unit derived from at least one kind of α-olefin having 2 to 20 carbon atoms is preferably 8.5 mol%, more preferably 8 mol%, and the lower limit is preferably 1 mol%, more preferably. Is 2 mol%.

When each structural unit is in the above range, a molded product obtained from the 4-methyl-1-pentene polymer composition containing the 4-methyl-1-pentene polymer (A2) is excellent in heat resistance and transparency. .
The 4-methyl-1-pentene polymer (A2) according to the present invention has a melting point (Tm) measured by (c2) DSC of 160 to 240 ° C, preferably 165 to 240 ° C, more preferably 170 to 240 ° C. More preferably, it exists in the range of 175-238 degreeC.

  The 4-methyl-1-pentene polymer composition containing the 4-methyl-1-pentene polymer (A2) having a melting point (Tm) value in the above range is excellent in moldability, and from the polymer composition. The obtained molded body is excellent in heat resistance and transparency.

  Since the 4-methyl-1-pentene polymer (A2) is particularly excellent in heat resistance, mechanical properties and transparency, the resulting 4-methyl-1-pentene polymer composition is also heat resistant and mechanical. Excellent physical properties and transparency.

<4-Methyl-1-pentene copolymer (B)>
The 4-methyl-1-pentene copolymer (B) constituting the 4-methyl-1-pentene polymer composition of the present invention is characterized by satisfying the following requirements (o) to (q).

[Requirement (o)]
(O) The structural unit derived from 4-methyl-1-pentene is 60 to 79 mol%, and the structural unit derived from at least one kind of α-olefin having 2 to 4 carbon atoms is 40 to 21 mol% (provided that The total amount of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from the α-olefin is 100 mol%).

  The upper limit of the structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene copolymer (B) according to the present invention is preferably 78 mol%, more preferably 77 mol%, The lower limit is preferably 65 mol%, more preferably 68 mol%. The upper limit of the structural unit derived from the α-olefin having 2 to 4 carbon atoms is preferably 35 mol%, more preferably 32 mol%, and the lower limit is preferably 22 mol%, more preferably 25 mol%.

  When each structural unit is in the above range, the polymer composition containing the 4-methyl-1-pentene copolymer (B) is excellent in flexibility, transparency, and stress absorption, so that the polymer composition is also flexible. It tends to be excellent.

Suitable examples of the α-olefin having 2 to 4 carbon atoms contained in the 4-methyl-1-pentene copolymer (B) include ethylene, propylene, and 1-butene.
Of these, propylene is preferably used from the viewpoint of copolymerizability.

These α-olefins having 2 to 4 carbon atoms can be used alone or in combination of two or more.
The 4-methyl-1-pentene copolymer (B) according to the present invention may contain structural units derived from other polymerizable compounds as long as the object of the present invention is not impaired.

  As such other polymerizable compounds, the same compounds as those described in the above-mentioned 4-methyl-1-pentene polymer (A) may be contained, and the proportion of the structural units is also the same. It is a range.

[Requirement (p)]
(P) The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 0.5 to 5.0 dl / g, preferably 1.0 to 4.0 dl / g, more preferably 1.2 to 3 .5 dl / g.

The value of the intrinsic viscosity [η] can be adjusted by the amount of hydrogen added during the polymerization when the 4-methyl-1-pentene copolymer (B) is produced.
The 4-methyl-1-pentene copolymer (B) having an intrinsic viscosity [η] in the above range exhibits good fluidity during the production of the resin composition and during various moldings. 4-methyl-1-pentene polymer (A) or 4-methyl-1-pentene polymer (A1) and 4-methyl-1-pentene polymer (A2) obtained by mixing with 4-methyl-1-pentene polymer (A2) The 1-pentene polymer composition is excellent in moldability, and a molded body such as a film obtained from the composition exhibits good elongation and toughness, and is excellent in transparency.

[Requirement (q)]
(Q) The melting point (T _m ) measured by DSC is less than 110 ° C. or no melting point is observed.
When the 4-methyl-1-pentene copolymer (B) according to the present invention has a melting point (T _m ), the upper limit is preferably 100 ° C., more preferably 95 ° C., particularly preferably the melting point. It is a polymer that is not observed. The melting point (T _m ) is a value that varies depending on the stereoregularity of the polymer and the amount of α-olefin to be copolymerized, and is controlled and adjusted to a desired composition using an olefin polymerization catalyst described later. Is possible. The 4-methyl-1-pentene copolymer (B) having a melting point (T _m ) in the above range is preferable from the viewpoints of transparency and moldability, heat resistance, flexibility and impact resistance, The combined composition also tends to be excellent in transparency and stress absorption.

<Method for Producing 4-Methyl-1-pentene Polymer (A) and 4-Methyl-1-pentene Copolymer (B)>
4-methyl-1-pentene polymer (A) according to the present invention (including 4-methyl-1-pentene polymer (A1) and 4-methyl-1-pentene polymer (A2)) and 4 -Methyl-1-pentene copolymer (B) is a conventionally known olefin polymerization catalyst such as a vanadium catalyst, a titanium catalyst, a magnesium-supported titanium catalyst, International Publication No. 01/53369, International Publication No. 01/27124 pamphlet, Japanese Patent Application Laid-Open No. Hei 3-19396 or Japanese Patent Application Laid-Open No. Hei 02-41303, and the like, 4-methyl-1-pentene and the above-mentioned specific α-olefin, and further necessary Depending on the above, it can be obtained by polymerizing the other polymerizable compound. Further, as the 4-methyl-1-pentene polymer (A), a general commercially available 4-methyl-1-pentene polymer can be used. As an example, TPX (manufactured by Mitsui Chemicals, Inc.) Registered trademark) can be used.

  Among the above-mentioned catalysts for olefin polymerization, a metallocene catalyst is preferably used as an embodiment of the catalyst for producing the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B). Can be mentioned.

  As preferred metallocene catalysts, as described above, WO 01/53369 pamphlet, WO 01/27124 pamphlet, JP-A-3-193396, JP-A-02-41303, or WO 06/1303. The metallocene catalyst described in the pamphlet of No. 0255540 is mentioned.

  In the present invention, the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B) are described above with 4-methyl-1-pentene in the presence of a metallocene catalyst. When producing using a specific α-olefin, the α-olefin introduced into the molecule tends to be introduced relatively randomly. In such a case, the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B) have a low melting point with a small amount of α-olefin. It is thought that the chain of pentene units becomes long and the compatibility with 4-methyl-1-pentene copolymer is good. Furthermore, when 4-methyl-1-pentene copolymers are combined with each other, in addition to being excellent in transparency considered to be derived from good compatibility, the crystal component can take a microcrosslinked structure, Excellent balance with mechanical properties. Although this characteristic is excellent in compatibility with the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B), they are not completely compatible. It is presumed that. A composition having such a compatible state is considered to be compatible at a high level without spoiling the characteristics of each component.

Hereinafter, the metallocene catalyst preferably used for production of the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B) according to the present invention will be described.
For the production of the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B) according to the present invention, (α) in the following general formula (1) or (2): A metallocene compound represented by (β) (β-1) an organometallic compound, (β-2) an organoaluminum oxy compound, and (β-3) a compound that reacts with the metallocene compound (α) to form an ion pair, A metallocene catalyst composed of at least one compound selected from the above, and (γ) a particulate carrier is used as necessary.

[(Α) metallocene compound]
In the present invention, the metallocene compound that can be used for the production of the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B) includes the following general formula (1) or ( The compound represented by 2) can be illustrated.

（上記一般式（１）または（２）中、Ｒ¹〜Ｒ¹⁴で表される置換基は水素原子、炭化水素基、ケイ素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、Ｒ¹からＲ⁴までの隣接した置換基は互いに結合して環を形成してもよく、Ｒ⁵からＲ¹²までの隣接した置換基は互いに結合して環を形成してもよく、Ａは一部不飽和結合および／または芳香族環を含んでいてもよい炭素原子数２〜２０の２価の炭化水素基であり、ＡはＹと共に形成する環を含めて２つ以上の環構造を含んでいてもよく、Ｍは周期表第４族から選ばれた金属であり、Ｙは炭素またはケイ素であり、Ｑはハロゲン、炭化水素基、アニオン配位子または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んでもよく、ｊは１〜４の整数である。）

(In the general formula (1) or (2), the substituent represented by R ^{1 to} R ¹⁴ is selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different, Adjacent substituents from R ¹ to R ⁴ may be bonded to each other to form a ring, adjacent substituents from R ⁵ to R ¹² may be bonded to each other to form a ring, and A is A divalent hydrocarbon group having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and A represents two or more ring structures including a ring formed with Y; M is a metal selected from Group 4 of the periodic table, Y is carbon or silicon, and Q can be coordinated by a halogen, a hydrocarbon group, an anionic ligand or a lone electron pair. You may choose from the same or different combination from a neutral ligand, and j is an integer of 1-4.

In R ^{1 to} R ^{14 of the} general formula (1) or (2), the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or the number of carbon atoms. It is a 6-20 aryl group or a C7-20 alkylaryl group, and may contain one or more ring structures. Further, a part or all of the hydrocarbon group may be substituted with a functional group such as a hydroxyl group, an amino group, a halogen group, or a fluorine-containing hydrocarbon group. Specific examples include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, biphenyl, naphthyl, tolyl, Chlorophenyl, chlorobiphenyl, chlorona Chill, and the like.

In R ^{1 to} R ^{14 of the} general formula (1) or (2), the silicon-containing hydrocarbon group is preferably an alkylsilyl group or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms. Specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl and the like.

Adjacent substituents from R ⁵ to R ¹² on the fluorene ring may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

The substituents R ⁵ to R ¹² on the fluorene ring are symmetrical from the viewpoint of ease of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , R ⁸ = R ⁹ . Preferably, it is unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Wherein the 3-position on the fluorene ring, 6-position, 2-position, 7-position corresponds to the ^{R 7, R 10, R 6} , R 11 , respectively.

R ¹³ and R ^{14 in} the general formula (1) are selected from a hydrogen atom or a hydrocarbon group, and may be the same or different. Specific examples of preferred hydrocarbon groups include those similar to the above R ^{1 to} R ¹⁴ .

Y is a carbon atom or a silicon atom. In the case of general formula (1), R ¹³ and R ¹⁴ are bonded to Y to form a substituted methylene group or a substituted silylene group as a bridging part. Preferred examples include, for example, methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, fluoromethylphenylmethylene, chloromethylphenylmethylene, diphenylmethylene, dichlorophenylmethylene, difluorophenyl. Methylene, methylnaphthylmethylene, dibiphenylmethylene, di-p-methylphenylmethylene, methyl-p-methylphenylmethylene, ethyl-p-methylphenylmethylene, dinaphthylmethylene or dimethylsilylene, diisopropylsilylene, methyl-tert-butylsilylene, Dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, fluoro Chill silylene, chloromethyl silylene, diphenyl silylene, mention may be made of di-p- methylphenyl silylene, methyl -p- methylphenyl silylene, ethyl -p- methylphenyl silylene, methyl naphthyl silylene, a dinaphthyl silylene like.

  In the case of the general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and a cycloalkylidene group or It constitutes a cyclomethylenesilylene group and the like. Preferable specific examples include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroin Examples include danylidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like.

M in the general formulas (1) and (2) is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium, and hafnium.
Q is selected from the same or different combinations from halogen, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. Specific examples of the halogen include fluorine, chlorine, bromine, and iodine. Specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, Q may be the same or different combinations, but at least one is preferably a halogen or an alkyl group.

[Compound (β)]
The compound (β) is selected from an organometallic compound (β-1), an organoaluminum oxy compound (β-2), and a compound (β-3) that reacts with the metallocene compound (α) to form an ion pair. It is composed of at least one compound.

Hereinafter, each component will be specifically described.
<< Organometallic Compound (β-1) >>
Specific examples of the organometallic compound (β-1) used as necessary in the present invention include the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table. For example, (β-1a), (β-1b), (β-1c) and the like described below can be mentioned. In the present invention, the (β-1) organometallic compound does not include the (β-2) organoaluminum oxy compound described later.

(Β-1a): an organoaluminum compound represented by the general formula R ^a _m Al (OR ^b ) _n H _p X _q (In the formula, R ^a and R ^b each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same or different from each other, X represents a halogen atom, and m represents 0 < m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3)
(Β-1b): Complex alkylated product of Group 1 metal of the periodic table represented by the general formula M ² AlR ^a ₄ and aluminum. (Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms)
(Β-1c): a dialkyl compound of a Group 2 or Group 12 metal represented by the general formula R ^a R ^b M ³ . (In the formula, R ^a and R ^b each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, which may be the same or different from each other, and M ³ is Mg, Zn or Cd)

Examples of the organoaluminum compound belonging to (β-1a) include the following compounds.
General formula R ^a _m Al (OR ^b ) _3-m (wherein R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other. M is preferably a number of 1.5 ≦ m ≦ 3.), An organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein R ^a is 1 to 1 carbon atoms) 15, preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m is preferably 0 <m <3.) An organoaluminum compound represented by the general formula R ^a _m AlH _{3− m} (wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3), a general formula during _{^{R a m Al (oR b)}} n X q ( wherein, R ^a and R ^b are optionally carbon atoms be the same or different from each other 1 15, preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3).

More specifically, as the organoaluminum compound belonging to (β-1a), trimethylaluminum, triethylaluminum, tri (n-butyl) aluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecyl Tri (n-alkyl) aluminum such as aluminum; triisopropylaluminum, triisobutylaluminum, tri (sec-butyl) aluminum, tri (tert-butyl) aluminum, tri (2-methylbutyl) aluminum, tri (3-methylbutyl) aluminum , Tri (2-methylpentyl) aluminum, tri (3-methylpentyl) aluminum, tri (4-methylpentyl) aluminum, tri (2-methylhexyl) Aluminum, tri (3-methylhexyl) aluminum, tri branched-chain alkyl aluminum such as tri (2-ethylhexyl) aluminum;
Tricyclohexyl aluminum, tri-cycloalkyl aluminum such as tri-cyclooctyl aluminum; triphenyl aluminum, triaryl aluminum such as tri-tolyl aluminum, diethyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum _{hydride; (iC 4 H 9) x} Al y (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers and z ≧ 2x. IC ₄ H ₉ represents an isobutyl group) Alkenyl aluminum;
Alkyl aluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; Ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide R ^a _2.5 Al (OR ^b ) _0.5 (wherein R ^a and R ^b are carbon atoms having 1 to 15 carbon atoms, which may be the same as or different from each other, preferably 1 to 4 carbon atoms). A partially alkoxylated alkylaluminum having an average composition represented by, for example: diethylaluminum phenoxide, diethylal Ni (2,6-di-tert-butyl 4-methylphenoxide), ethylaluminum bis (2,6-di-tert-butyl 4-methylphenoxide), diisobutylaluminum (2,6-di-tert-butyl 4- Dialkylaluminum aryloxides such as methylphenoxide) and isobutylaluminum bis (2,6-di-tert-butyl4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, etc. Dialkylaluminum halides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide Halides; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; ethylaluminum dihydride; Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as propylaluminum dihydride; partially alkoxylated and halogenated alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxycycloride, ethylaluminum ethoxybromide Aluminum etc. are mentioned.

Moreover, the compound similar to ((beta) -1a) can also be used, for example, the organoaluminum compound which two or more aluminum compounds couple | bonded through the nitrogen atom is mentioned. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .
Examples of the compound belonging to (β-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Examples of the compound belonging to (β-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, and butylethylmagnesium.
Examples of (β-1) organometallic compounds other than the above (β-1a) to (β-1c) include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethyl Magnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

A compound that can form the organoaluminum compound in the multimerization reaction system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used.
Of the organometallic compounds (β-1), organoaluminum compounds are preferred. The organometallic compound (β-1) as described above is used singly or in combination of two or more.

<< Organic Aluminum Oxygen Compound (β-2) >>
The organoaluminum oxy compound (β-2) used as necessary in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum exemplified in JP-A-2-78687. It may be an oxy compound.

  A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon. (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (β-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The organoaluminum compound (β-2) as described above is used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  In the benzene-insoluble organoaluminum oxy compound (β-2) used in the present invention, the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% in terms of Al atoms. The following are preferable, that is, insoluble or hardly soluble in benzene.

  Examples of the organoaluminum oxy compound (β-2) used in the present invention also include an organoaluminum oxy compound containing boron represented by the following general formula (i).

式（ｉ）中、Ｒ¹⁵は炭素原子数が１〜１０の炭化水素基を示す。Ｒ¹⁶は、互いに同一でも異なっていてもよい水素原子、ハロゲン原子、炭素原子数が１〜１０の炭化水素基を示す。

In the formula (i), R ¹⁵ represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹⁶ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other.

The organoaluminum oxy compound containing boron represented by the general formula (i) includes an alkyl boronic acid represented by the following general formula (ii) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. In particular, it can be produced by reacting at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.
R ¹⁵ —B (OH) ₂ ... (Ii) (In the formula (ii), R ¹⁵ is selected from the same group as in the above formula (i)).

Specific examples of the alkyl boronic acid represented by the general formula (ii) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, and n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid, and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable.
These may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (β-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.
The above organoaluminum oxy compounds (β-2) are used singly or in combination of two or more.

<< Compound that reacts with metallocene compound (α) to form ion pair (β-3) >>
The compound (β-3) that reacts with the metallocene compound (α) to form an ion pair and is used as necessary in the present invention is a compound that reacts with the metallocene compound (α) to form an ion pair. Therefore, what forms an ion pair by making it contact with a metallocene compound ((alpha)) at least is contained in this compound.

  Examples of such compounds include JP-A-1-501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, and JP-A-3. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 207704 and US Pat. No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group) can be mentioned. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (P-Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like can be mentioned.
Examples of the ionic compound include compounds represented by the following general formula (iii).

式（ｉｉｉ）中、Ｒ¹⁷⁺としては、Ｈ⁺、カルボニウムカチオン、オキソニウムカチオン、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などが挙げられる。
Ｒ¹⁸〜Ｒ²¹は、互いに同一でも異なっていてもよい有機基、好ましくはアリール基または置換アリール基である。
前記カルボニウムカチオンとして具体的には、トリフェニルカルボニウムカチオン、トリ（メチルフェニル）カルボニウムカチオン、トリ（ジメチルフェニル）カルボニウムカチオンなどの三置換カルボニウムカチオンなどが挙げられる。

In formula (iii), ^examples of R ¹⁷⁺ include H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.
R ^{18 to} R ²¹ are organic groups which may be the same as or different from each other, preferably an aryl group or a substituted aryl group.
Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N, 2,4,6-pentamethylanilinium cation and the like N, N-dialkylanilinium cation; di (isopropyl) ammonium cation, dicyclohexylammonium cation and the like dialkylammonium cation Etc.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ¹⁷⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tri (n-propyl) ammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetra (p-tolyl) borate, Trimethylammonium tetra (o-tolyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, tri (n-propyl) ammonium tetra (o, p-dimethylphenyl) borate, tri (n-butyl) ammonium Tetra (m, m-dimethylphenyl) borate, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetra (3,5-dito Trifluoromethylphenyl) borate, tri (n- butyl) ammonium tetra (o-tolyl) borate.

  Specific examples of N, N-dialkylanilinium salts include, for example, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N, 2,4,6-pentamethylaniline. Examples thereof include nium tetraphenylborate.

  Specific examples of the dialkylammonium salt include di (n-propyl) ammonium tetra (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

  Further, as the ionic compound (β-3), triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, tri Examples thereof include phenyl carbenium pentaphenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (iv) or (v).

（式（ｉｖ）中、Ｅｔはエチル基を示す。）

(In the formula (iv), Et represents an ethyl group.)

ボラン化合物として具体的には、例えばデカボラン（１４）；ビス〔トリ（ｎ−ブチル）アンモニウム〕ノナボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕デカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ウンデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ドデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕デカクロロデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ドデカクロロドデカボレートなどのアニオンの塩；トリ（ｎ−ブチル）アンモニウムビス（ドデカハイドライドドデカボレート）コバルト酸塩（ＩＩＩ）、ビス〔トリ（ｎ−ブチル）アンモニウム〕ビス（ドデカハイドライドドデカボレート）ニッケル酸塩（ＩＩＩ）などの金属ボランアニオンの塩などが挙げられる。

Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undeca Salts of anions such as borate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

  Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecarborane (14), dodecahydride-1-phenyl-1, 3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,7-dicarbaound decaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, (N-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) Ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7 carbaundecaborate (13), tri (n-butyl) ammonium 7 , 8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydra Id-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride 8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4, Salts of anions such as 6-dibromo-7-carbaundecaborate; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaoundecabo Acid) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undeca) Hydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n -Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaun) Decaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl) Til-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbundecaborate) cobaltate (III), tris [ Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate ) Manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis ( Metal carbonates such as undecahydride-7-carbaundecaborate) nickelate (IV) Such as the salt of the run-anion, and the like.

  The heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, lintongost vanadic acid, germanotangostovanadic acid, phosphomolybdotangostobanamic acid, germanomolybdo tungstovanadate, phosphomolybdo Tungstic acid, phosphomolybniobic acid, salts of these acids, such as metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium , With barium etc. Salts, and organic salts such as triphenylethyl salt, and isopoly compound can be used but not limited thereto.

The heteropoly compound and the isopoly compound are not limited to one of the above compounds, and two or more of them can be used.
The compound (β-3) that forms an ion pair by reacting with the metallocene compound (α) as described above is used alone or in combination of two or more.

(Polymerization conditions)
In the present invention, polymerization of 4-methyl-1-pentene and the like can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods. In the liquid phase polymerization method, an inert hydrocarbon solvent may be used. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, lichloromethane and tetrachloromethane or mixtures thereof And so on. Bulk polymerization using olefins containing 4-methyl-1-pentene as a solvent can also be carried out.

  In addition, so-called multistage polymerization in which the polymerization conditions are changed stepwise can also be performed. For example, a desired broad molecular weight distribution or a wide composition distribution of 4-by-step polymerization is carried out by carrying out polymerization stepwise under two conditions with different amounts of hydrogen used or the ratio of 4-methyl-1-pentene and α-olefin. It is also possible to obtain a methyl-1-pentene polymer (A) and a 4-methyl-1-pentene copolymer (B). In addition, 4-methyl-1-pentene system in which the composition distribution is controlled by performing stepwise homopolymerization of 4-methyl-1-pentene and copolymerization of 4-methyl-1-pentene with other olefins. It is also possible to obtain a polymer (A) and a 4-methyl-1-pentene copolymer (B).

In carrying out the polymerization, the component (α) is usually 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ mol in terms of Group 4 metal atom in the periodic table per liter of reaction volume. Used in various amounts.

  When the component (β) is used, the component (β-1) is a molar ratio of the component (β-1) to the transition metal atom (M) in the component (α) [(β-1) / M. ] Is usually used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000.

  In the component (β-2), the molar ratio [(β-2) / M] of the aluminum atom in the component (β-2) and the transition metal atom (M) in the component (α) is usually 10 to 10. The amount used is 500,000, preferably 20 to 100,000.

The component (β-3) has a molar ratio [(β-3) / M] of the component (β-3) and the transition metal atom (M) in the component (α) of usually 1 to 10, preferably It is used in such an amount as to be 1-5.
The polymerization temperature is usually in the range of −50 to 200 ° C., preferably 0 to 100 ° C., more preferably 20 to 100 ° C. If the polymerization temperature is too low, there is an industrial disadvantage in terms of polymerization activity per unit catalyst and heat recovery efficiency.

  The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. In the polymerization, hydrogen can be added for the purpose of controlling the molecular weight and polymerization activity of the produced polymer, and the amount is suitably about 0.001 to 100 NL per kg of olefin.

[Softener (C)]
As the softening agent (C) constituting the 4-methyl-1-pentene polymer composition of the present invention, a conventionally known softening agent can be used. Specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt and petroleum jelly; coal tars such as coal tar and coal tar pitch; castor oil, linseed oil, Fat oils such as rapeseed oil, soybean oil and coconut oil; waxes such as tall oil, beeswax, carnauba wax and lanolin; ricinoleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, montanic acid, oleic acid and elca Fatty acids such as acids or their metal salts; petroleum resins, coumarone indene resins and atactic polypropylene; liquids such as liquid polybutene, liquid polybutadiene, liquid ethylene / α-olefin copolymers, liquid ethylene / propylene / diene copolymers Olef Liquid oligomers, liquid styrene oligomers, liquid acrylic polymers, liquid polyurethanes, synthetic polymers and oligomers; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; other microcrystalline waxes, or Examples thereof include modified products or hydrogenated products; liquid thiocol.

<4-Methyl-1-pentene polymer composition>
The 4-methyl-1-pentene polymer composition of the present invention is 10 to 100 parts by mass, preferably 15 to 100 parts by mass, and more preferably 25 to 100 parts by mass of the 4-methyl-1-pentene copolymer (A). 100 parts by mass, 0-90 parts by mass of the 4-methyl-1-pentene copolymer (B), preferably 0-85 parts by mass, more preferably 0-75 parts by mass [However, (A) component and (B ) The total of the components is 100 parts by mass. And the total of the component (A) and the component (B) is 100 parts by mass, the softening agent (C) is 5 to 150 parts by mass, preferably 5 to 100 parts by mass, more preferably 10 to 10 parts by mass. It is a composition containing 70 parts by mass.

  When the content of the softening agent (C) contained in the 4-methyl-1-pentene polymer composition is in the above range, the molded product obtained from the 4-methyl-1-pentene polymer composition has a low temperature. This is preferable because the property, flexibility, and stress absorption are improved.

  A composition having a softener (C) content of less than 5 parts by mass may deteriorate the low-temperature properties of a molded product obtained from the composition. When the content exceeds 150 parts by mass, the softener (C) is 4 -The softening agent oozes out without being completely impregnated in the methyl-1-pentene polymer composition, and the surface stickiness and optical properties of the resulting molded article may be deteriorated.

  When the 4-methyl-1-pentene polymer composition of the present invention contains the 4-methyl-1-pentene copolymer (B), it is obtained from the 4-methyl-1-pentene polymer composition. The stress absorbability of the resulting molded product is further improved.

  As the 4-methyl-1-pentene polymer composition of the present invention, as the 4-methyl-1-pentene copolymer (A), the 4-methyl-1-pentene polymer (A1) and the 4 When the methyl-1-pentene polymer (A2) is used in combination, the mass ratio [(A1) / (A2)] is usually 95/5 to 5/95, preferably 90/10. To 10/90, more preferably 85/15 to 15/85. When the 4-methyl-1-pentene polymer (A1) and the 4-methyl-1-pentene polymer (A2) are used in combination, the resulting 4-methyl-1-pentene polymer composition The molded body obtained from the product is particularly excellent in heat resistance.

  Further, as the 4-methyl-1-pentene polymer composition of the present invention, the 4-methyl-1-pentene polymer (A1) is used as the 4-methyl-1-pentene copolymer (A). It is a preferred embodiment to combine the 4-methyl-1-pentene copolymer (B), and in that case, the mass ratio [(A1) / (B)] is usually 10/90 to 60 / 40, preferably 15/85 to 60/40, more preferably in the range of 25/75 to 60/40.

  When the 4-methyl-1-pentene polymer (A1) is in the above range, a 4-methyl-1-pentene polymer composition containing the 4-methyl-1-pentene polymer (A1). The molded product obtained from is improved in the balance between heat resistance and stress absorption.

[Other ingredients]
In the 4-methyl-1-pentene polymer composition of the present invention, an antioxidant, a heat stabilizer, a weather stabilizer, an antistatic agent, if necessary, as long as the object of the present invention is not impaired. Anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, dyes, pigments, anti-aging agents, hydrochloric acid absorbents, crystal nucleus materials, waxes, fillers, flame retardants and the like can be blended.

  A known antioxidant can be used as the antioxidant. Specifically, a hindered phenol compound, a sulfur-based antioxidant, a lactone-based antioxidant, an organic phosphite compound, an organic phosphonite compound, or a combination of these can be used.

  Examples of the lubricant include sodium, calcium and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid and stearic acid, and these may be used alone or in combination of two or more. it can. Moreover, the compounding quantity of this lubricant is 0.1-3 mass parts normally with respect to 100 mass parts of 4-methyl-1-pentene polymer compositions, Preferably it is about 0.1-2 mass parts. Is desirable.

  Examples of the anti-blocking agent include fine powder silica, fine powder aluminum oxide, fine powder clay, powdered or liquid silicon resin, tetrafluoroethylene resin, fine powder cross-linked resin such as cross-linked acrylic and methacrylic resin powder. be able to. Of these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferred.

The 4-methyl-1-pentene polymer composition of the present invention preferably satisfies the following requirements (x1) and (x2).
(X1) The internal haze measured with a 1 mm thick press sheet is in the range of 0.01-20.
(X2) The maximum value of loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s in the temperature range of −40 ° C. to 150 ° C. is 0.7 to 5.0, and the value of tan δ is The maximum temperature is in the range of -40 ° C to 40 ° C.
Hereinafter, the requirements (x1) to (x2) will be described.

[Requirement (x1)]
The internal haze of a 1 mm thick press sheet obtained from the 4-methyl-1-pentene polymer composition of the present invention is in the range of 0.01 to 20, preferably 0.01 to 15, more preferably 0.01 to 10. It is in.

  The above range can be adjusted by the ratio and type of 4-methyl-1-pentene copolymer (A), 4-methyl-1-pentene copolymer (B) and softener (C) in the composition. The 4-methyl-1-pentene polymer composition having an internal haze value in the above range is well compatible with each other and tends to be excellent in transparency.

[Requirement (x2)]
The maximum value of loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s in the temperature range of −40 ° C. to 150 ° C. is 0.7 to 5.0, preferably 0.7 to 4.0. More preferably, it is 0.8-4.0. The temperature at which the value of tan δ is maximized is in the range of −40 ° C. to 40 ° C., preferably in the range of −30 ° C. to 40 ° C., more preferably in the range of −25 ° C. to 40 ° C.

  If the maximum value of tan δ is within these ranges, the 4-methyl-1-pentene polymer composition can exhibit excellent stress absorbability. The maximum value of tan δ is the amount of α-olefin contained in the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B), or 4-methyl in the composition. It can be controlled by the mixing ratio of the -1-pentene polymer (A) and other components.

  In the 4-methyl-1-pentene polymer composition of the present invention, the softening agent (C) is well compatible with the 4-methyl-1-pentene polymer (A), and 4-methyl-1 -When including the pentene copolymer (B), the 4-methyl-1-pentene polymer (A) having a higher melting point (Tm) than the 4-methyl-1-pentene copolymer (B), A 4-methyl-1-pentene copolymer (B) having a low melting point or no melting point is compatible with the 4-methyl-1-pentene polymer composition in the 4-methyl-1-pentene polymer composition. Since it is presumed that the coalesced (A) is moderately dispersed and has a micro-crosslinked structure, the heat resistance and stress absorption are maintained while maintaining excellent transparency unlike the composition with other thermoplastic resins. Both low temperature and low temperature. Further, the micro-crosslinking structure exhibits rubber elasticity such as tensile elasticity and stress relaxation, and suppresses bleed out of the softening agent.

<Method for producing 4-methyl-1-pentene polymer composition>
The 4-methyl-1-pentene polymer composition of the present invention is prepared by various known methods using the 4-methyl-1-pentene polymer (A), the 4-methyl-1-pentene copolymer ( Each component of B) and the softening agent (C) can be obtained in a predetermined amount and, if necessary, by mixing other components.

  As a mixing method of each component, specifically, for example, a multistage polymerization method, a plastmill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler, a blender, a kneader ruder, or the like, or after mixing, a single screw extruder A method of granulating or pulverizing after melt-kneading with a twin screw extruder, kneader, Banbury mixer or the like can be employed. It is also possible to employ a method in which a softening agent is added to the extruder during granulation by the extruder. By this method, a high-quality 4-methyl-1-pentene polymer composition in which each component and additive are uniformly dispersed and mixed can be obtained.

<Molded body comprising 4-methyl-1-pentene polymer composition>
The molded body containing the 4-methyl-1-pentene polymer composition of the present invention is, for example, film molding such as extrusion molding, injection molding, inflation film molding, T-die film molding, blow molding, extrusion blow molding, It can be obtained by known molding methods such as injection blow molding, press molding, stamping molding, vacuum molding, calendar molding, filament molding, foam molding, powder slush molding and the like.

<< Film / Sheet Consisting of 4-Methyl-1-Pentene Polymer Composition >>
Examples of the molded body containing the 4-methyl-1-pentene polymer composition of the present invention include films and sheets.

  In the 4-methyl-1-pentene polymer composition of the present invention, the 4-methyl-1-pentene polymer (A) and the softening agent (C) are compatible with each other. -When including the pentene copolymer (B), the 4-methyl-1-pentene polymer (A) having a higher melting point (Tm) than the 4-methyl-1-pentene copolymer (B), A 4-methyl-1-pentene copolymer (B) having a low melting point or no melting point is compatible with the 4-methyl-1-pentene polymer composition in the 4-methyl-1-pentene polymer composition. Since it is presumed that the coalesced (A) is dispersed and has a finely crosslinked structure, the film and sheet made of the copolymer composition are transparent and excellent in heat resistance, low temperature property and stress absorption.

  Moreover, by changing the composition ratio of the 4-methyl-1-pentene polymer (A) to be used, it is possible to control stress absorption and heat resistance, and to control flexibility by controlling the blending amount of the softener. It exhibits excellent properties at low temperatures. Further, the 4-methyl-1-pentene polymer composition has a feature that the stickiness of the film generated in the conventional composition is reduced by suppressing the above-mentioned bleed-out of the softening agent.

  In addition to the single layer film obtained from the 4-methyl-1-pentene polymer composition of the present invention, the film and sheet according to the present invention (hereinafter sometimes simply referred to as a film) are the present invention. It is also a preferred embodiment that the film is a laminated film including at least one film obtained from the 4-methyl-1-pentene polymer composition. As a method for obtaining such a laminated film, various known film forming methods can be used. Specifically, for example, the 4-methyl-1-pentene polymer of the present invention is formed on the surface layer of a film made of another thermoplastic polymer obtained by T-die film molding or blown film molding. A method of laminating the composition by a known laminating method such as extrusion lamination or extrusion coating, and coextrusion molding of the 4-methyl-1-pentene polymer composition of the present invention and another thermoplastic polymer using a multilayer die. And a method of laminating each film by dry lamination after obtaining a film using the 4-methyl-1-pentene polymer composition of the present invention and another thermoplastic polymer. Etc.

  As the preferred form, it can be suitably used as a multi-layered surface protective film comprising the film of the present invention in the film surface layer. Moreover, it can utilize suitably as a material which makes an adhesion layer and a shock absorption layer compatible by making use of the adhesiveness which 4-methyl-1- pentene copolymer (B) has.

<Application>
The 4-methyl-1-pentene polymer composition of the present invention and a molded article made of the polymer composition have a feature that the peak value of tan δ is large, and is excellent in heat resistance, transparency, and low temperature properties. Demonstrate the characteristics. Therefore, it is particularly useful for applications such as shock absorbing members that require damping properties, seismic isolation, and the like, and is also useful for design because of its transparency.

  Specific examples of shock absorbing members include health products, nursing care products (eg, fall prevention films, mats and sheets), shock absorbing pads, protectors / protectors (eg, helmets, guards), and sports equipment (eg, sports grips). ), Sport armor, rackets, balls, transport equipment (eg, shock absorbing grip for transport, shock absorbing sheet), health equipment, industrial materials (eg, vibration damping pallet, shock absorbing damper, shock absorbing member for footwear, shock) Absorbent foams, impact absorbing films and sheets), automobile impact absorbing members (eg, bumper impact absorbing members, cushion members) and the like.

  Specific examples of films and sheets containing the 4-methyl-1-pentene polymer composition of the present invention include packaging films and sheets, automobile member films and sheets, industrial films and sheets, agricultural and civil engineering films. And sheets, films for medical use and cell culture, films and sheets for members of electrical and electronic equipment, films and sheets for household goods, and the like. Furthermore, it is suitably used for impact protection films such as displays that make use of transparency and impact absorption.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the examples, each physical property was measured as follows.
[Intrinsic viscosity [η]]
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of polymer powder, pellets or resin mass was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was obtained as the intrinsic viscosity (see the following formula).
[Η] = lim (ηsp / C) (C → 0)

[MFR]
The MFR of the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B) is a load of 5 kg at 260 ° C. or 230 ° C. according to JIS K7210. Measured with a load of 16 kg. The propylene polymer was measured under the conditions of 230 ° C. and 2.16 kg load.

[Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B) were measured by gel permeation chromatography manufactured by Waters. Using a graph Alliance GPC-2000, measurement was performed as follows.

The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o -Using dichlorobenzene (Wako Pure Chemical Industries) and 0.025 wt% BHT (Takeda Pharmaceutical) as an antioxidant, moving at 1.0 ml / min, sample concentration 15 mg / 10 mL, sample injection volume 500 micron A differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

[4-methyl-1-pentene and α-olefin content in polymer]
Quantification of 4-methyl-1-pentene and α-olefin content in the polymer was carried out from the results of measurement by ¹³ C-NMR using the following apparatus and conditions.

Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a solvent mixture of orthodichlorobenzene / heavy benzene (80/20% by volume), sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration number is 10,000 times or more, and 27.50 ppm is the reference value for chemical shift As measured. From the obtained 13C-NMR spectrum, the composition of 4-methyl-1-pentene and α-olefin was quantified.

[Melting point ( _Tm )]
The melting point (Tm) of the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (B) was measured using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc. About 5 mg of sample is packed in a pan, heated to 250 ° C. at 10 ° C./minute, held at 250 ° C. for 5 minutes, then lowered to −50 ° C. at 10 ° C./minute, and then at 10 ° C./minute. The melting point (T _m ) was calculated from the peak apex of the crystal melting peak when the temperature was raised to 250 ° C. When the polymer had a plurality of peaks, the peak apex located on the highest temperature side was defined as the melting point (Tm).

[Methods for manufacturing various measurement sheets]
Kamito in which 4-methyl-1-pentene polymer (A), 4-methyl-1-pentene copolymer (B) and 4-methyl-1-pentene polymer composition were set to 200 to 260 ° C. Sheet forming was performed at a gauge pressure of 10 MPa by using a hydraulic hot press machine (NS-50) manufactured by Metal Industry Co., Ltd. In the case of a sheet having a thickness of 1 to 3 mm (spacer shape; 200 × 200 × 1 to 2 mm on a 240 × 240 × 2 mm thick plate), preheating is performed for about 5 to 7 minutes, and the gauge pressure is 10 MPa for 1 to 2 minutes. Then, using another hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set to 20 ° C., it was compressed at a gauge pressure of 10 MPa and cooled for about 5 minutes to prepare a measurement sample. A 5 mm thick brass plate was used as the hot plate. The samples prepared by the above method were used for various physical property evaluation samples.

[density]
For the density measurement, the 1 mm-thick press sheet obtained by the above method was cut into 30 mm square, and was measured by an underwater substitution method using an electronic hydrometer according to JIS K6268.

[Dynamic viscoelasticity measurement]
The tan δ peak value and the peak temperature were determined by cutting the 3 mm-thick press sheet obtained by the above method into 45 mm × 10 mm, and using an ANTONPaar MCR301 with a dynamic viscosity of −40 to 150 ° C. at a frequency of 10 rad / s. The temperature dependence of elasticity was measured.

[Internal haze (%)]
The internal haze was measured with a digital turbidimeter (NDH-20D) manufactured by Nippon Denshoku Industries Co., Ltd. in benzyl alcohol using the 1 mm-thick press sheet obtained by the above method as a test piece.

[Low temperature]
The low temperature property is confirmed by using the 1 mm-thick press sheet obtained by the above method as a test piece, cutting it to 38 mm × 5 mm, and the temperature at which 50% of the total number of the test pieces breaks in accordance with ASTM D746. Was measured. From this result, the number of fractures of the test piece when tested at 0 ° C. is described as follows.
○: All were not destroyed (low temperature property at 0 ° C. was good).
X: 50% or more of the total number was destroyed.

[Heat-resistant]
For heat resistance, a 1 mm-thick press sheet obtained by the above method was cut into a length of 50 × 10 mm and used as a test piece. The sample was suspended in a hot air dryer at 80 ° C. for 24 hours and stored, and the dimensional change of the test piece before and after storage was confirmed. In particular, the heat resistance at 80 ° C. was described as follows from the length of change in the vertical direction.
○: No change in shape (good heat resistance at 80 ° C.)
Δ: Shape change of 5 mm or less occurred.
X: A shape change of 5 mm or more occurred.

[Tensile rubber elasticity]
Tensile rubber elasticity was obtained by cutting out a 1 mm thick press sheet obtained by the above method into 50 × 10 × 10 mm as a test piece. After extending 20% by hand in the vertical direction at room temperature of 23 ° C., the condition until the hand was released and allowed to return to its original length was confirmed and described as follows.
○: Returned quickly to the original length ± 5 mm in the vertical direction.
Δ: It took time, but the original length returned to the range of ± 5 mm.
X: It did not return to the original length.

[Synthesis Example 1] Production of 4-methyl-1-pentene polymer (A) [Synthesis Example 1-1] Production of 4-methyl-1-pentene copolymer (A1-1)
A SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently purged with nitrogen was charged with 300 ml of normal hexane at 23 ° C. (dried in a dry nitrogen atmosphere and activated alumina) and 450 ml of 4-methyl-1-pentene. . The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

  Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.19 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.01 mmol of dichloride into the autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected 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 powdered polymer containing the solvent was dried at 100 ° C. under reduced pressure for 12 hours. The obtained polymer was 44.0 g, and the 4-methyl-1-pentene content in the polymer was 84.1 mol% and the propylene content was 15.9 mol%. The melting point (T _m ) of the polymer was 132 ° C., and the intrinsic viscosity [η] was 1.5 dl / g.
Table 1 shows the measurement results of various physical properties.

[Synthesis Example 1-2] Production of 4-methyl-1-pentene copolymer (A2-1) To a 1.5-liter SUS autoclave with a stirring blade sufficiently purged with nitrogen, the 4-methyl-1 was added at 23 ° C. -750 ml of pentene was charged. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

  Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.15 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.005 mmol of dichloride into an autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected 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 powdery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The obtained polymer was 45.9 g, and the 4-methyl-1-pentene content in the polymer was 92.3 mol% and the propylene content was 7.7 mol%. The melting point (T _m ) of the polymer was 178 ° C., and the intrinsic viscosity [η] was 1.6 dl / g.
Table 1 shows the measurement results of various physical properties.

[Synthesis Example 1-3] Production of 4-methyl-1-pentene copolymer (A2-2) According to the method of Comparative Example 7 and Comparative Example 9 of International Publication No. 2006/054613, 4-methyl 1-pentene By changing the ratio of 1-decene and hydrogen, 4-methyl-1-pentene copolymer (A2-2) having the physical properties shown in Table 1 was obtained.

[Synthesis Example 2] Production of 4-methyl-1-pentene copolymer (B) [Synthesis Example 2-1] Production of 4-methyl-1-pentene copolymer (B-1) Capacity 1 sufficiently substituted with nitrogen A 5 liter SUS autoclave with a stirring blade was charged with 300 ml of normal hexane (dried on a dry nitrogen atmosphere and activated alumina) and 450 ml of 4-methyl-1-pentene at 23 ° C. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

  Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.40 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.01 mmol of dichloride into the autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected 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 powdered polymer containing the solvent was dried at 100 ° C. under reduced pressure for 12 hours. The obtained polymer was 36.9 g, and the 4-methyl-1-pentene content in the polymer was 72.5 mol% and the propylene content was 27.5 mol%. The melting point (T _m ) of the polymer was not observed, and the intrinsic viscosity [η] was 1.5 dl / g.
Table 1 shows the measurement results of various physical properties.

[Example 1]
With respect to 100 parts by mass of the 4-methyl-1-pentene polymer (A1-1) obtained in Synthesis Example 1-1, a mineral oil-based process oil (produced by Idemitsu Kosan Co., Ltd., a product) 15 parts by weight of PW-90) and 0.2 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer . Thereafter, using a twin screw extruder BT-30 (screw system 30 mmφ, L / D = 46) manufactured by Plastic Engineering Laboratory Co., Ltd. under the conditions of a set temperature of 280 ° C., a resin extrusion rate of 60 g / min and 200 rpm. The pellet for evaluation was obtained by granulation.
Table 2-1 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

[Example 2]
25 parts by mass of 4-methyl-1-pentene polymer (A1-1) obtained in Synthesis Example 1-1 and 4-methyl-1-pentene copolymer (B-1) 75 obtained in Synthesis Example 2-1 Part by mass, total amount of (A1-1) and (B-1): Mineral oil-based process oil (trade name PW-90, manufactured by Idemitsu Kosan Co., Ltd.) as a softener (C) with respect to 100 parts by mass 15 parts by mass were mixed, the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain pellets for evaluation.
Table 2-1 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

[Example 3]
25 parts by weight of 4-methyl-1-pentene polymer (A1-1) obtained in Synthesis Example 1-1 and 4-methyl-1-pentene copolymer (B-1) 75 obtained in Synthesis Example 2-1. Part by mass, total amount of (A1-1) and (B-1): Mineral oil-based process oil (trade name PW-90, manufactured by Idemitsu Kosan Co., Ltd.) as a softener (C) with respect to 100 parts by mass 30 parts by mass were mixed, the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain pellets for evaluation.
Table 2-1 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

[Example 4]
25 parts by mass of 4-methyl-1-pentene polymer (A1-1) obtained in Synthesis Example 1-1 and 4-methyl-1-pentene copolymer (B-1) 75 obtained in Synthesis Example 2-1 Part by mass, total amount of (A1-1) and (B-1): Mineral oil-based process oil (made by Idemitsu Kosan Co., Ltd., trade name NS-90S) as a softener (C) with respect to 100 parts by mass 15 parts by mass were mixed, the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain pellets for evaluation.
Table 2-1 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

[Example 5]
40 parts by mass of 4-methyl-1-pentene polymer (A1-1) obtained in Synthesis Example 1-1 and 4-methyl-1-pentene copolymer (B-1) 60 obtained in Synthesis Example 2-1. Part by mass, total amount of (A1-1) and (B-1): Mineral oil-based process oil (trade name PW-90, manufactured by Idemitsu Kosan Co., Ltd.) as a softener (C) with respect to 100 parts by mass 15 parts by mass were mixed, the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain pellets for evaluation.
Table 2-1 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

[Reference Example 6]
25 parts by mass of 4-methyl-1-pentene polymer (A2-1) obtained in Synthesis Example 1-2 and 4-methyl-1-pentene copolymer (B-1) 75 obtained in Synthesis Example 2-1 Mass part, total amount of (A2-1) and (B-1): Mineral oil-based process oil (made by Idemitsu Kosan Co., Ltd., trade name PW-100) as softener (C) with respect to 100 parts by mass 15 parts by mass were mixed, the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain evaluation pellets.
Table 2-1 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

[Reference Example 7]
10 parts by mass of 4-methyl-1-pentene polymer (A2-2) obtained in Synthesis Example 1-3 and 4-methyl-1-pentene copolymer (B-1) 90 obtained in Synthesis Example 2-1. Mass part, total amount of (A2-2) and (B-1): Mineral oil-based process oil (made by Idemitsu Kosan Co., Ltd., trade name PW-100) as softener (C) with respect to 100 parts by mass 15 parts by weight was mixed, the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain pellets for evaluation.
Table 2-1 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

[Reference Example 8]
10 parts by mass of 4-methyl-1-pentene polymer (A2-2) obtained in Synthesis Example 1-3 and 4-methyl-1-pentene copolymer (B-1) 90 obtained in Synthesis Example 2-1. 15 parts by mass of liquid polybutene (manufactured by JX Nippon Mining & Energy Corporation, trade name HV-100) as a softener (C) with respect to 100 parts by mass. After mixing by mass, the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain pellets for evaluation.
Table 2-2 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

[Reference Example 9]
10 parts by mass of 4-methyl-1-pentene polymer (A2-2) obtained in Synthesis Example 1-3 and 4-methyl-1-pentene copolymer (B-1) 90 obtained in Synthesis Example 2-1. Mass part, total amount of (A2-2) and (B-1): liquid ethylene / α-olefin copolymer (trade name: Lucant HC, manufactured by Mitsui Chemicals) as softener (C) with respect to 100 parts by mass -150) was mixed, 15 parts by mass of the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain pellets for evaluation.
Table 2-2 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

[Comparative Example 1]
Using 100 parts by mass of 4-methyl-1-pentene polymer (B-1) obtained in Synthesis Example 2-1, the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions. Thus, an evaluation pellet was obtained.
Table 2 shows the measurement results of various physical properties of the sheet obtained by molding the pellets under the above conditions.

[Comparative Example 2]
Mineral oil-based process oil (made by Idemitsu Kosan Co., Ltd., trade name PW) as a softener (C) with respect to 100 parts by mass of 4-methyl-1-pentene polymer (A2-1) obtained in Synthesis Example 1-2 -90) was mixed, 15 parts by mass of the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain pellets for evaluation.
The results of measuring various physical properties of the sheet obtained by molding the pellets under the above conditions are shown in Table 2-2.

[Comparative Example 3]
25 parts by mass of 4-methyl-1-pentene polymer (A2-1) obtained in Synthesis Example 1-2 and 4-methyl-1-pentene copolymer (B-1) 75 obtained in Synthesis Example 2-1 Mass parts were mixed, the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain pellets for evaluation.
Table 2-2 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

[Comparative Example 4]
60 parts by mass of 4-methyl-1-pentene copolymer (B-1) obtained in Synthesis Example 2-1 and 40 parts by mass of ethylene / α-olefin copolymer (trade name TAFMER A0550S manufactured by Mitsui Chemicals, Inc.) Were mixed, the same amount of heat stabilizer as in Example 1 was blended, and extrusion granulation was performed under the same conditions to obtain pellets for evaluation.
Table 2-2 shows the measurement results of various physical properties of films obtained by molding the pellets under the above conditions.

Claims (4)

10 to 100 parts by mass of 4-methyl-1-pentene polymer (A) satisfying the following requirements (a) to (c) and 4-methyl-1-pentene satisfying the following requirements (o) to (q) 90 to 0 parts by mass of copolymer (B) (however, the total of component (A) and component (B) is 100 parts by mass), and the total amount of component (A) and component (B) A 4-methyl-1-pentene polymer composition comprising 5 to 150 parts by mass of the softening agent (C) with respect to 100 parts by mass.
(A) The structural unit derived from 4-methyl-1-pentene is 80 mol% or more and less than 91 mol%, and the structural unit derived from at least one of α-olefins having 2 to 20 carbon atoms exceeds 9 mol%. It exists in the range of 20 mol% or less [However, the total amount of the structural unit derived | led-out from 4-methyl-1-pentene and the structural unit derived | led-derived from an alpha olefin shall be 100 mol%. ].
(B) The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is in the range of 0.5 to 5.0 dl / g.
(C) The melting point (Tm) measured by DSC is in the range of 110 ° C to 160 ° C.
(O) The structural unit derived from 4-methyl-1-pentene is derived from at least one of α-olefins (excluding 4-methyl-1-pentene) having 79 to 60 mol% and 2 to 4 carbon atoms. The structural unit is in the range of 40 to 21 mol% [however, the total amount of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from the α-olefin is 100 mol%. ].
(P) The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is in the range of 0.5 to 5.0 dl / g.
(Q) The melting point (Tm) measured by DSC is less than 110 ° C. or no melting point is observed. The 4-methyl-1-pentene polymer composition according to claim 1, which satisfies the following requirements.
(X1) The internal haze value of the 1 mm thick press sheet is in the range of 0.01-20.
(X2) The maximum value of loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s in the temperature range of −40 ° C. to 150 ° C. is 0.7 to 5.0, and the value of tan δ is The maximum temperature is in the range of -40 ° C to 40 ° C.   A molded article comprising the 4-methyl-1-pentene polymer composition according to claim 1.   A film or sheet comprising the 4-methyl-1-pentene polymer composition according to claim 1.